New insights into magma dynamics during last two eruptions of Mount Etna as inferred by geochemical monitoring from 2002 to 2005

Two distinct eruptive events characterize the volcanic activity at Mount Etna during the 2002 to 2005 period. We identified signals of magma ascent preceding these eruptions by geochemical monitoring of both chemical composition and He-isotope ratio of gas emissions from five locations in the peripheral area of the volcano. The geochemical signals are interpreted using the models proposed by Caracausi et al. (2003a, 2003b) and allow identification of episodes of magma ascent and estimation of the pressures of degassing magma. As observed for the 2001 eruption (Caracausi et al., 2003b), magma ascent probably triggered the onset of the 2002–2003 eruption, and minor events of magma ascent were…

Molecular and isotopic composition of free hydrocarbon gases from Sicily, Italy

[1] Chemical and isotopic data have been used as geochemical tracers for a genetic characterization of hydrocarbon gases from a total of eleven manifestations located in Eastern and Central-Southern Sicily (Italy). The molecular analysis shows that almost all the samples are enriched in methane (up to 93.2% Vol.), with the exception of four gas samples collected around Mt. Etna showing high mantle-derived CO2 content. Methane isotope signatures suggest that these are thermogenic gases or a mixture between thermogenic gases and microbial gases. Although samples from some mud volcanoes in Southern Sicily (Macalube di Aragona) show isotope signatures consistent with a mixing model between ther…

Application of Geostatistical Tools to the Geochemical Characterization of the Peloritani Mts (Sicily, Italy) Aquifers

Sources of groundwater contaminants in inhabited areas, located in complex geo-tectonic contexts, are often deeply interlocked, thus, making the discrimination between anthropic and natural origins difficult. In this study, we investigate the Peloritani Mountain aquifers (Sicily, Italy), using the combination of probability plots with concentration contour maps to retrieve an overall view of the groundwater geo-chemistry with a special focus on the flux of heavy metals. In particular, we present a methodology for integrating spatial data with very different levels of precision, acquired before and during the “geomatic era”. Our results depict a complex geochemical layout driven by a geo-puz…

Geochemistry and potential use of groundwater in the Rocca Busambra area (Sicily, Italy)

In the Rocca Busambra area (mid-west Sicily, Italy), from November 1999 to July 2002, 23 water points including wells and springs were sampled and studied for their chemical and isotopic compositions. Two rain gauges were also installed at different altitudes, and rainwater was collected monthly to determine the isotopic composition. The obtained results revealed the Rocca Busambra carbonate complex as being the main recharge area on account of its high permeability value. From a chemical view point, two main groups of water can be distinguished: calcium–magnesium–bicarbonate-type and calcium–magnesium–chloride–sulphate-type waters. The first group reflects the dissolution of the carbonate …

Rates of carbon dioxide plume degassing from Mount Etna volcano,

We report here on the real-time measurement of CO2 and SO2 concentrations in the near-vent volcanic gas plume of Mount Etna, acquired by the use of a field portable gas analyzer during a series of periodic field surveys on the volcano's summit. During the investigated period (September 2004 to September 2005), the plume CO2/SO2 ratio ranged from 1.9 to 10.8, with contrasting composition for Northeast and Voragine crater plumes. Scaling the above CO2/SO2 ratios by UV spectroscopy determined SO2 emission rates, we estimate CO2 emission rates from the volcano in the range 0.9-67.5 kt d-1 (average, 9 kt d-1). About 2 kt of CO2 were emitted daily on average during quiescent passive degassing, wh…

Deformation history during chain building deduced by outcrop structural analysis: The case of the Sicilian fold-and-thrust belt (Central Mediterranean)

Abstract The Sicilian fold-and-thrust belt is located in the central Mediterranean area, and it represents the south-eastern arcuate segment of the Apennine-Maghrebide orogen. The tectonic evolution of the Sicilian belt is documented after outcrop analysis of small-scale structural features carried out throughout the region. Results are consistent with the following four main deformation stages having affected the study area, from the oldest to the youngest: (i) multilayer weakening; (ii) folding-and-thrusting, (iii) extension, and (iv) renewed thrusting. The first deformation stage included three different substages (layer-parallel shortening, bed-parallel simple shear and fold nucleation)…

Gas hazard assessment at the Monticchio crater lakes of Mt. Vulture, a volcano in Southern Italy

Geochemical investigations have shown that there is a considerable inflow of gas into both crater lakes of Monticchio, Southern Italy. These lakes are located in two maars that formed 140 000 years ago during Mt. Vulture volcanos last eruptive activity. Isotopic analyses suggest that CO2 and helium are of magmatic origin; the latter displays 3 He ⁄ 4 He isotope ratios similar to those measured in olivines of the maar ejecta. In spite of the fact that the amount of dissolved gases in the water is less than that found in Lake Nyos (Cameroon), both the results obtained and the historical reports studied indicate that these crater lakes could be highly hazardous sites, even though they are loca…

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 Caste…

Isotopic composition of the precipitations in the central Mediterranean: Origin marks and orographic precipitation effects

The isotopic composition of the rainfall in northwestern Sicily (Italy, central Mediterranean) was investigated in the period February 2002 to March 2003. A rain gauge network was installed and sampled monthly. The monthly values of the D and 18O ratios showed a wide range that reflected seasonal climatic variations. Mean weighted values were used to define an isotopic model of precipitation. Temporal variations in deuterium excess were also investigated. Using mean volume weighted values, the Local Meteoric Water Line (LMWL) can be represented by the equation: δD = 4.7δ18O - 8.2 (r2 = 0.96). Deuterium excess (d = δD - 8δ18O) was found to be strongly related to orography. The coastline samp…

Mount Etna: Geochemical signals of magma ascent and unusually extensive plumbing system

] FiveyearsofgasmonitoringfromselectedsitessuggestthatMtEtna’splumbingsystemismuchmoreextensivethanpreviously reported. It extends at least 40 km SW from thevolcano’s boundary along the NE-SW regional fault, whereit discharges about 200 tons/day of gas, containing heliumwith mantle-type isotopic composition. Synchronousvariations of

Hydrochemical evolution and environmental features of Salso River catchment, central Sicily (Italy)

A hydrogeochemical study of the Salso River highlighted the chemical and isotopic space-time evolution along its flow path and the main contamination processes. Within the basin, three different hydrogeochemical facies have been individuated: (1) Ca-Mg-HCO3, (2) Ca-Mg-SO4 and (3) Na-Cl. The first facies reflects the chemical composition of the groundwaters hosted in the carbonate reliefs that belong to the Madonie Mountains. The second and the third facies are the result of the interaction processes between surface waters and the gypsum and salty clays, respectively. Two pollution sources have been also located in the basin downstream from the salt mine and downstream from a discharge area …

A regional-scale discontinuity in western Sicily revealed by a multidisciplinary approach: A new piece for understanding the geodynamic puzzle of the southern Mediterranean

The results of an integrated stratigraphic, structural, geophysical, and geochemical study reveal the presence of a crustal discontinuity in western Sicily that, at present, runs roughly N-S along a band from San Vito Lo Capo to Sciacca (SVCS). The boundary between the two zones of this discontinuity is nearly orthogonal to the main thrust propagation of the Sicilian thrust-and-fold belt. The different Permian to Tertiary sedimentary evolution recorded by the two zones appears related to this discontinuity, with thick carbonate platforms in the western sector facing deep-water successions in the eastern one. The presence of Upper Triassic reefs, huge megabreccias bodies, and widespread subm…

The use of shallow dripwater as an isotopic marker of seepage in karst areas: A comparison between Western Sicily (Italy) and the Harz Mountains (Germany)

Abstract The isotopic signature of slow-flowing dripwater collected in caves located in Western Sicily (Italy) was determined for evaluating its possible use as an isotopic tracer of the local groundwater recharge. These spot measures were compared with a longer series of local rain and spring compositions and with other samples taken, under different hydrogeological conditions, in caves of the Harz Mountains (Northern Germany). The slow flowing dripwater from Sicily showed δ 18 O/δD ratios similar to those of local rain and groundwater, demonstrating that these three are all parent waters. A parallel similarity was found in the vertical isotopic gradient (Δδ 18 O) of the three groups of wa…

Isotopic composition of single rain events in the central Mediterranean

[1] The ratios of stable isotopes of single rain events were investigated during the period October 2005 to September 2006 in the central Mediterranean. Clear seasonal trends were identified in both oxygen isotope ratios and the deuterium-excess parameter, and these were ascribed to the dominant circulation systems during both cold and hot intraannual periods. Rain events were classified on the basis of the origin of rain-bearing systems. Air masses coming from the south usually give rise to rainwater with a low deuterium excess. Air masses coming from the north and the northeast are often dry and cold, and are associated with high evaporation from the Mediterranean Sea that occurs under is…

Mud volcanoes as key-systems to investigate continental degassing and therole of seismicity on mass transfer

The flow of fluids into the Earth’s crust can produce large-scale heat and mass transport. The mechanisms and driving forces for this fluid-transport range from molecular diffusion, to grain boundary diffusion and to advective flow. Recent studies [Torgersen,2010 and references therein] suggest that largescale vertical transport of fluids in the continental crust is likely advective and episodic. So it is crucial to understand if the variability of the measured degassing flux is a reflection of this episodic and advective transport. Here we try to answer these questions by using the noble gases. In particularly He that is recognized as a powerful tracer in variousfields, such as hydrology, …

Modeling Rain Isotopic Composition under Orographic Control: A Landscape Approach for Hydrogeological Applications

Oxygen isotopic composition is useful for individuating recharge areas of groundwater bodies by the comparison with those of local rainfalls. While on a global scale general relationships, such as the isotopic vertical gradient or continentality effects, efficiently describe spatial variations of the isotopic signature, hydrogeological applications need spatial models that are more focused on the effects of local topographic structures and/or subsoil geology. This work presents a case study in northeastern Sicily (Italy) characterized by complex geological and orographic structures, in which isotopic composition of rainfalls is governed by orographic effects and the varying initial composit…

Tectonic evolution of the Sicilian Thrust System (central Mediterranean)

The Sicilian Thrust System (STS) is a south-verging (Africa-verging) fold-and-thrust belt including a Mesozoic-Paleogene sedimentary sequence. This thrust stack owes its origin to the deformation of pre-orogenic strata deposited in different palaeogeographic domains belonging to passive margins of the African plate. The STS was deformed during the Neogene, following the closure of the Tethys Ocean and the continental collision between the Sardo-Corso Block and the North Africa margins. The thrust pile was detached from the underlying basement during the Miocene-Pleistocene. The regional-scale structural setting recognized allows us to reconstruct the tectonic evolution of the STS as follows…

Continental degassing of helium in an active tectonic setting (northern Italy): the role of seismicity

AbstractIn order to investigate the variability of helium degassing in continental regions, its release from rocks and emission into the atmosphere, here we studied the degassing of volatiles in a seismically active region of northern Italy (MwMAX = 6) at the Nirano-Regnano mud volcanic system. The emitted gases in the study area are CH4–dominated and it is the carrier for helium (He) transfer through the crust. Carbon and He isotopes unequivocally indicate that crustal-derived fluids dominate these systems. An high-resolution 3-dimensional reconstruction of the gas reservoirs feeding the observed gas emissions at the surface permits to estimate the amount of He stored in the natural reserv…

Interaction between the deep fluids and the shallow groundwaters on Vulcano island (Italy)

The aim of this work is to study the interactions processes between the fluids of deep origin and the shallow groundwaters of the Vulcano Porto area. During 1995, 13 well waters were sampled three times (May, July and November) and analysed for major and some minor elements (B, Br and NH4) and for dissolved gases. The close relationship of these waters with the deep magmatic source is highlighted by the composition of the dissolved gases. Furthermore, the areal distribution of dissolved species is controlled mainly by the gas fluxes from depth and by the presence of a deeper thermal aquifer. The distribution of major anomalies in the parameters measured in the groundwaters, in fact, overlap…

Distribution of volatile organic compounds in Sicilian groundwaters analysed by head space-solid phase micro extraction coupled with gas chromatography mass spectrometry (SPME/GC/MS).

This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710km (2)). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both …

Isotope composition of rain water, well water and fumarole steam on the island of Vulcano, and their implications for volcanic surveillance

Abstract Water samples from eight wells in the Vulcano Porto area and fumarole steam from the crater of Vulcano (Southern Italy) were collected at monthly intervals over a two-year period from February 1987 to January 1989. Samples of bulk precipitation were also collected in three points at Vulcano Porto and Vulcano Piano (island of Vulcano) and Castroreale (Tyrrhenian coast of Sicily), again at monthly intervals. The weighted mean isotopic composition of rain water on Vulcano is δ D =−32‰ , and δ D 18 O =−6.4‰ . Results for well waters tend to support the existence of at least two water bodies: one of purely meteoric water and the other of brackish thermal water. An intermediate water bod…

Flow changes and geochemical anomalies in warm and cold springs associated with the 1992-1994 seismic sequence at Pollina, Central Sicily, Italy

During a three-year discontinuous geochemical monitoring of some warm springs and cold discharges located in central-northern Sicily, some hydro-geochemical changes were observed. Excluding a possible related to a moderate seismic activity were accidentally identified. The observed anomalies showed amplitudes that were modulated by the different geometries and volumes of the feeding aquifers. A poroelastic aquifer contraction, a shaking-induced dilatancy theory as well as seismogenetic-induced changes in the properties of the aquifers have been proposed as possible mechanisms for the water flow and hydro-geochemical changes. These preliminary results could be used to design a monitoring net…

Genesis of fumarolic emissions as inferred by isotope mass balances: CO 2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period fro…

Geophysical contribution to the reconstruction of the hydrological model of "Barcellona-Milazzo plain" groundwater body, northen Sicily

The “Barcellona-Milazzo plain” groundwater body in the northen Sicily, was analysed in detail, through numerous geophysical measurements that were integrated with stratigraphic data in order to reconstruct the hydrological model. The “Barcellona-Milazzo plain” (BMP) groundwater body has been identified within the coastal sector between the village of Oliveri, to the west, and Capo Rasocolmo, to the east. It also includes several rivers that rise further south in correspondence with the Peloritani ridge and flow into the wide Barcellona-Milazzo alluvial plain. On the basis of several geophysical and geological data analysis and interpretation have been used to reconstruct the composition and…

Lower pleistocene deposits in east part of the Favignana island, Sicily, Italy

Geochemical insight into differences in the physical structures and dynamics of two adjacent maar lakes at Mt. Vulture volcano (southern Italy)

[1] We report on the first geochemical investigation of the Monticchio maar lakes (Mt. Vulture volcano, southern Italy) covering an annual cycle that aimed at understanding the characteristic features of the physical structures and dynamics of the two lakes. We provide the first detailed description of the lakes based on high-resolution conductivity-temperature-depth (CTD) profiles, chemical and isotopic (H and O) compositions of the water, and the amounts of dissolved gases (e.g., He, Ar, CH4, and CO2). The combined data set reveals that the two lakes, which are separated by less than 200 m, exhibit different dynamics: one is a meromictic lake, where the waters are rich in biogenic and man…

Groundwater nitrate risk assessment using intrinsic vulnerability methods: A comparative study of environmental impact by intensive farming in the Mediterranean region of Sicily, Italy

Abstract Groundwater contamination by nitrate and other nutrients is a major problem throughout the world, often occurring as the result of anthropogenic activities, lack of management, and over-exploitation of groundwater resources. In the last few decades in the majority of the Italian regions, the nitrate concentrations in groundwater have dramatically increased, mainly as a consequence of the large-scale agricultural application of manure and fertilizers. This excessive use of chemicals and fertilizers increases the risk of surface and groundwater pollution from diffuse sources, which have an important impact on human health and the environment. Sicily is located in the central Mediterr…

Moisture source in the Hyblean mountains region (south-eastern Sicily,Italy):Evidence from stable isotopes signature

Abstract Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line ( δD  = 6.50 δ 18 O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average 2 H excess value of +21.2‰ was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O…

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…

Geochemical monitoring of groundwaters (1998-2001) at Vesuvius volcano (Italy)

This work presents the results of hydrogeochemical studies carried out at Vesuvius during the period May 1998-December 2001, mostly focusing on compositional time variations observed during this time. Based on their chemistry, groundwater samples are distinguished into two groups, 1 and 2, representative of water circulation in the southern and northern sectors of the volcano, respectively. Waters from group 1 are typically more acidic, warmer, and more saline than those of group 2. They also have higher CO2 and CH4 contents, attributed to enhanced input of deep-rising volatiles and prolonged water-rock interactions. Time-series highlight the fairly constant chemical composition of the enti…

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below t…

Mineral control of arsenic content in thermal waters from volcano-hosted hydrothermal systems: Insights from island of Ischia and Phlegrean Fields (Campanian Volcanic Province, Italy)

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 690…

Extensional deformations during Neogene chain building in Sicily

ABSTRACT In the Madonie-Nebrodi Mts (Northern Sicily belt) both Mesozoic carbonate platform/basin-derived deformed successions and Neogene foredeep deposits outcrop. Thrust sheets piled-up southwards in thin-skin piggy-back sequence. The chain building process began during the Oligo-Miocene. The syntectonic deposits involved in the compressional tectonics give evidence that syn-sedimentary extensional faults developed during fold nucleation and amplification. Syn-sedimentary extensional faults affect the foredeep strata at different stratigraphic levels, which are bounded by unconformities. Normal faults and bedding show constant cut-off relationships and are progressively tilted youngwards…

Active geodynamics of the central Mediterranean Sea: Tensional tectonic evidences in western Sicily from mantle-derived helium

[1] We report results on the measured high 3He/4He isotope ratio in western Sicily, interpreted together with the heat data. The study of this sector of the Europe-Africa interaction is crucial to a better understanding of the tectonics and the geodynamical evolution of the central Mediterranean area. The estimated mantle-derived helium fluxes in the investigated areas are up to 2–3 orders of magnitude greater than those of a stable continental area. The highest flux, found in the southernmost area near the Sicily Channel, where recent eruptions of the Ferdinandea Island occurred 20 miles out to sea off Sciacca, has been associated with a clear excess of heat flow. Our results indicate that…