Relationships between diffuse CO 2 emissions and volcanic activity on the island of Vulcano (Aeolian Islands, Italy) during the period 1984-1994

Measurements of CO2 flux from the ground were periodically carried out on the island of Vulcano (Aeolian Islands, Italy) between 1984 and 1994. Three high-flux areas were identified at the foot of the volcanic cone (La Fossa), either inside or very close to the main village. Effect of the choice of the sampling grid was evaluated. A different sampling grid resulted in similar distribution patterns, but with different CO2 fluxes. Therefore, the absolute estimate of the total flux from the investigated area includes a large degree of uncertainty, but repeated measurements with permanent sampling sites are accurate and can detect small changes. No correlation of the flux with atmospheric param…

CO2flux measurements in volcanic areas using the dynamic concentration method: Influence of soil permeability

[1] In order to evaluate the influence of soil permeability on soil CO2 flux measurements performed with the dynamic concentration method, several tests were carried out using soils characterized by different permeability values and flow rates. A special device was assembled in the laboratory to create a one-dimensional gas flow through a soil of known permeability. Using the advective-diffusion theory, a physical model to predict soil concentration gradients was also developed. The calculated values of CO2 concentrations at different depths were compared with those measured during the tests and a good agreement was found. Four soils with different gas permeability (3.6 × 10−2 to 1.23 × 102…

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…

Chemical and isotopic characterization of the gases of Mount Etna (Italy)

Abstract In the period 1990–1995, 43 samples of dissolved gases in groundwaters (wells, springs and drainage galleries) and 64 samples of free gases (fumaroles, bubbling and soil gases) from the Mount Etna area were collected and analysed. Isotopic analyses were also carried out of both the carbon of the CO 2 in free gases and dissolved inorganic carbon (DIC) in the waters. The chemical composition of the gases depends on the relative abundances of three interacting components. These are gases of (1) atmospheric origin enriched in O 2 and N 2 , present almost exclusively in dissolved gases, (2) deep origin enriched in CO 2 , prevalent in the majority of cases, and (3) more superficial origi…

First observational evidence for the CO<sub>2</sub>-driven origin of Stromboli's major explosions

Abstract. We report on the first detection of CO2 flux precursors of the till now unforecastable "major" explosions that intermittently occur at Stromboli volcano (Italy). An automated survey of the crater plume emissions in the period 2006–2010, during which 12 such explosions happened, demonstrated that these events are systematically preceded by a brief phase of increasing CO2/SO2 weight ratio (up to >40) and CO2 flux (>1300 t d−1) with respect to the time-averaged values of 3.7 and ~500 t d−1 typical for standard Stromboli's activity. These signals are best explained by the accumulation of CO2-rich gas at a discontinuity of the plumbing system (decreasing CO2 emission at the surfa…

Asynchronous changes of CO2, H2, and He concentrations in soil gases: A theoretical model and experimental results

Emission of bromine and iodine from Mount Etna volcano

[1] Constraining fluxes of volcanic bromine and iodine to the atmosphere is important given the significant role these species play in ozone depletion. However, very few such measurements have been made hitherto, such that global volcanic fluxes are poorly constrained. Here we extend the data set of volcanic Br and I degassing by reporting the first measurements of bromine and iodine emissions from Mount Etna. These data were obtained using filter packs and contemporaneous ultraviolet spectroscopic SO2 flux measurements, resulting in time-averaged emission rates of 0.7 kt yr−1 and 0.01 kt yr−1 for Br and I, respectively, from April to October 2004, from which we estimate global Br and I flu…

Trace metal modeling of groundwater–gas–rock interactions in a volcanic aquifer: Mount Vesuvius, Southern Italy

We report a detailed study of trace metals in groundwaters from the Somma-Vesuvius volcanic complex and present a model of the chemical processes that control the fate of these components during gas–water–rock interactions. Trace metal concentrations in Vesuvian groundwaters range from 0.01 to 0.1 Ag/l for ultra-trace elements (Sb, Cs, Co, Cd, and Pb) up to 0.1–10 mg/l for minor elements (Fe and Sr), leading to water–rock ratios from ~0.5 to 10 � 9 when normalized to trace element concentrations in the host rocks. Our results indicate non-isochemical dissolution of local volcanic rocks by groundwaters, during which mobile trace elements (As, Se, Mo, V, Li) are enriched and elements such as …

Geochemical investigations applied to active fault detection in a volcanic area: the North-East Rift on Mt. Etna (Sicily, Italy)

Geochemical investigations were performed on the Northeast Rift of Mt. Etna, a prominent volcanic structure of this volcano. Low-temperature fumaroles were found on the upper part of this area and the isotopic compositions of C(CO2) and He suggest a likely magmatic origin of the emitted gases. On the contrary, very low degassing was found in the lower part of the NE-Rift, with CO2 concentrations generally very close to those in air. This pattern is probably due to sealing of the eruptive fissures by the repeated injections of magma solidified into dikes and by consequent shallow hydrothermal alteration of the fissured rocks due to residual magma degassing. High soil CO2 concentrations were …

The 2007 eruption of Stromboli volcano: Insights from real-time measurement of the volcanic gas plume CO2/SO2 ratio

Abstract The recent eruption of Stromboli in February–April 2007 offered a unique chance to test our current understanding of processes driving the transition from ordinary (persistent Strombolian) to effusive activity, and the ability of instrumental geophysical and geochemical networks to interpret and predict these events. Here, we report on the results of two years of in-situ sensing of the CO 2 /SO 2 ratio in Stromboli's volcanic gas plume, in the attempt to put constraints on the trigger mechanisms and dynamics of the eruption. We show that large variations of the plume CO 2 /SO 2 ratio (range, 0.9–26) preceded the onset of the eruption (since December 2007), interrupting a period of …

Forecasting Etna eruptions by real-time observation of volcanic gas composition

It is generally accepted, but not experimentally proven, that a quantitative prediction of volcanic eruptions is possible from the evaluation of volcanic gas data. By discussing the results of two years of real-time observation of H2O, CO2, and SO2 in volcanic gases from Mount Etna volcano, we unambiguously demonstrate that increasing CO2/SO2 ratios can allow detection of the pre-eruptive degassing of rising magmas. Quantitative modeling by the use of a saturation model allows us to relate the pre-eruptive increases of the CO2/SO2 ratio to the refilling of Etna's shallow conduits with CO2-rich deep-reservoir magmas, leading to pressurization and triggering of eruption. The advent of real-ti…

Effects of soil gas permeability and recirculation flux on soil CO2 flux measurements performed using a closed dynamic accumulation chamber

Abstract Dynamic accumulation chamber methods have been extensively used to estimate the total output of CO2 released from active volcanic area. In order to asses the performance and reliability of a closed dynamic system several tests were carried out with different soil permeabilities and soil CO2 fluxes. A special device was used to create a constant one-dimensional CO2 flux through a soil column with a known permeability. Three permeabilities were investigated, ranging between 3.6 × 10− 2 and 3.5 × 10 μm2, as were several CO2 fluxes (ranging between 1.1 × 10− 6 and 6.3 × 10− 5 kg m− 2 s− 1). The results highlight that the accuracy of soil CO2 flux measurements strictly depends on the so…

Variation of H2O/CO2and CO2/SO2ratios of volcanic gases discharged by continuous degassing of Mount Etna volcano, Italy

[1] We applied the Multi-GAS technique to measure compositions of the volcanic plumes continuously discharged from summit craters of Voragine, Northeast and Bocca Nuova at Mount Etna, in an attempt to estimate compositions of the source volcanic gases. The estimated CO2/SO2 and H2O/CO2 ratios of the volcanic gases show a large variation ranging from 0.6 to 30 and from 1 to 18, respectively. This variability overlaps with the compositional range of dissolved volatiles in melt inclusions and their coexisting bubbles in a magma chamber and can be caused by the low-pressure degassing of a magma with variable bubble content ranging from 0.3 to 15 wt.%. The variable bubble content in the magma is…

Hydrologic and geochemical survey of the lake ‘‘Specchio di Venere’’ (Pantelleria island, Southern Italy)

Hydrological and geochemical studies performed on Lake Specchio di Venere on Pantelleria island (Italy) indicate that this endorheic basin has been formed through upwelling of the water table, and that it is continuously fed by the thermal springs situated on its shores. The lake is periodically stratified both thermally and in salinity, albeit this stratification is rather unstable over time, since meteorological events such as strong rain or wind can determine the mixing of its waters. Periodical analyses of the lake water chemistry show large variations of the salt content due to the yearly evaporation-rain dilution cycle. These processes are also responsible for the saline stratificatio…

Insights into magma and fluid transfer at Mount Etna by a multiparametric approach: A model of the events leading to the 2011 eruptive cycle

[1] Since the second half of the 1990s, the eruptive activity of Mount Etna has provided evidence that both explosive and effusive eruptions display periodic variations in discharge and eruption style. In this work, a multiparametric approach, consisting of comparing volcanological, geophysical, and geochemical data, was applied to explore the volcano's dynamics during 2009–2011. In particular, temporal and/or spatial variations of seismicity (volcano-tectonic earthquakes, volcanic tremor, and long-period and very long period events), ground deformation (GPS and tiltmeter data), and geochemistry (SO2 flux, CO2 flux, CO2/SO2 ratio) were studied to understand the volcanic activity, as well as…

Total volatile flux from Mount Etna

[1] The Total Volatile (TV) flux from Mount Etna volcano has been characterised for the first time, by summing the simultaneously-evaluated fluxes of the three main volcanogenic volatiles: H2O, CO2 and SO2. SO2 flux was determined by routine DOAS traverse measurements, while H2O and CO2 were evaluated by scaling MultiGAS-sensed H2O/SO2 and CO2/SO2 plume ratios to the UV-sensed SO2 flux. The time-averaged TV flux from Etna is evaluated at ∼21,000 t·day−1, with a large fraction accounted for by H2O (∼13,000 t·day−1). H2O dominates (≥70%) the volatile budget during syn-eruptive degassing, while CO2 and H2O contribute equally to the TV flux during passive degassing. The CO2 flux was observed to…

Continuous monitoring of hydrogen and carbon dioxide at Mt Etna

article i nfo This study assessed the use of an H2 fuel cell as an H2-selective sensor for volcano monitoring. The resolution, repeatability, and cross-sensitivity of the sensor were investigated and evaluated under known laboratory conditions. A tailor-made device was developed and used for continuously monitoring H2 and CO2 at Mt Etna throughout 2009 and 2010. The temporal variations of both parameters were strongly correlated with the evolution of the volcanic activity during the monitoring period. In particular, the CO2 flux exhibited long-term variations, while H2 exhibited pulses immediately before the explosive activity that occurred at Mt Etna during 2010.

Soil CO2 degassing on Mt Etna (Sicily) during the period 1989?1993: discrimination between climatic and volcanic influences

Wide variations were measured in the diffuse CO2 flux through the soils in three selected areas of Mt Etna between August 1989 and March 1993. Degassing of CO2 from the area of Zafferana Etnea-S. Venerina, on the eastern slope of the volcano, has been determined to be more strongly influenced by meteorological parameters than the other areas. The seasonal component found in the data from this area has been excluded using a filtering algorithm based on the best fitting equation calculated from the correlation between CO2 flux values and those of air temperature. The filtered data appear to have variations temporally coincident with those from the other areas, thus suggesting a common and pro…

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…

Anomalous soil CO 2 degassing in relation to faults and eruptive fissures on Mount Etna (Sicily, Italy)

The relationships between soil gas emissions and both tectonic and volcano-tectonic structures on Mt. Etna have been studied. The investigation consisted of soil CO2 flux measurements along traverses orthogonal to the main faults and eruptive fissures of the volcano. Anomalous levels of soil degassing were found mainly in coincidence with faults, whereas only 49% of the eruptive fissures were found to produce elevated CO2 soil fluxes. This result suggests that only zones of strain are able to channel deep gases to the surface. According to this hypothesis, several previously unknown structures are suggested. Based on our geochemical data, new structural maps of different areas of Etna are p…

Crustal dynamics of Mount Vesuvius from 1998 to 2005: Effects on seismicity and fluid circulation

[1] This paper presents the results of hydrogeochemical and seismological studies carried out at Mount Vesuvius during the period June 1998 to December 2005. Hydrogeochemical data show the occurrence of slowly varying long-term variations in the total dissolved salts and bicarbonate contents of the groundwaters, accompanied by a general decline in water temperatures. The temporal distributions of air temperature and rainfall in the Vesuvius area suggest that these variations do not depend on changes in the hydrological regime. The changes in the geochemical parameters are accompanied by slight variations in both the seismicity rate and energy release. A further relationship between seismic …

Plume chemistry provides insights into mechanisms of sulfur and halogen degassing in basaltic volcanoes

Abstract This paper deals with sulfur, chlorine and fluorine abundances in the eruptive volcanic plume of the huge October 2002–January 2003 eruption of Mount Etna, aiming at relating the relevant compositional variations observed throughout with changes in eruption dynamics and degassing mechanisms. The recurrent sampling of plume acidic volatiles by filter-pack methodology revealed that, during the study period, S/Cl and Cl/F ratios ranged from 0.1–6.8 and 0.9–5.6, respectively. Plume S/Cl ratios increased by a factor of ∼10 as volcanic activity drifted from paroxysmal lava fountaining (mid- and late November) to passive degassing and minor effusion (early January), and then decreased to …

Tectonic control over large-scale diffuse degassing in eastern Sicily (Italy)

Eastern Sicily (southern Italy) is characterised by the presence of many natural gas emissions (mofettes, mud volcanoes). These gases are mostly carbon dioxide and methane, with minor amounts of helium, hydrogen, carbon monoxide and hydrocarbons. In this study, the extent and orientation of soil gas anomalies (He and CO2) were investigated on a wide area (approximately 110 km2) located just SW of Mt. Etna. From a structural point of view, this area lays on a typical foredeep–foreland system that marks the boundary between the southern part of the Eurasian plate and the northern part of the African plate in the central Mediterranean. No tectonic structure was revealed in this area by surface…

Hydrothermal buffering of the SO2/H2S ratio in volcanic gases: Evidence from La Fossa Crater fumarolic field, Vulcano Island

[1] Sulfur speciation in volcanic gases is a potentially valuable tracer of degassing processes at volcanoes. Hitherto, observations of sulfur speciation in volcanic gas plumes have however been limited both in number and quality. Here, we report on periodic measurements of SO2 to H2S proportions in the volcanic gases from La Fossa volcano (Vulcano Island) performed during 2004–2006, a period which encompasses two heating events of the fumarolic field in January–April 2005 and December 2005. Results indicate a systematic relative increase (by a factor of 2–6) of SO2 to H2S proportions in the fumaroles during the heating events, which we ascribe to a temperature increase in the mixing zone b…

Chemical mapping of a fumarolic field: La Fossa Crater, Vulcano Island (Aeolian Islands, Italy)

[1] The performance of a newly-developed portable gas analyzer, capable of real-time measurement of CO2, SO2 and H2S concentrations in volcanic gases, was tested at La Fossa Crater, Vulcano Island. The gas analyzer was used to acquire about 3000 determinations over the fumarolic field, allowing the definition of its chemical structure and heterogeneity. Our high-resolution analysis reveals that, in December 2004, the La Fossa fumarolic field was characterized by an oxidized inner core (SO2/H2S ratios of ∼3), and by more reducing conditions on its northern edge (SO2/H2S ratios of ∼1; range: 0.2–3.3). CO2/(SO2+H2S) molar ratios averaged 35 ± 21, with overlapping compositions for rim and inner…

Soil CO2 degassing along tectonic structures of Mount Etna (Sicily): the Pernicana fault

Abstract Carbon dioxide emissions from the soil have been investigated along lines of equally spaced sampling points perpendicular to the Pernicana fault on Mt Etna. Anomalous values of soil CO2 have been found not only along the fault plane, but also along directions parallel to it, both to the N and to the S of the main fault. The acquired data seem to reveal a shallow step-like geometry of the Pernicana fault system with parallel faults being generally not deeper than the interface between Etna's volcanic cover and its sedimentary basement (a few hundred meters). The distribution of the anomalous CO2 emissions has also revealed that the Pernicana fault continues at least as far as the Io…

Tracking Formation of a Lava Lake From Ground and Space: Masaya Volcano (Nicaragua), 2014-2017

A vigorously degassing lava lake appeared inside the Santiago pit crater of Masaya volcano (Nicaragua) in December 2015, after years of degassing with no (or minor) incandescence. Here we present an unprecedented-long (3 years) and continuous volcanic gas record that instrumentally characterizes the (re)activation of the lava lake. Our results show that, before appearance of the lake, the volcanic gas plume composition became unusually CO 2 rich, as testified by high CO 2 /SO 2 ratios (mean: 12.2 ± 6.3) and low H 2 O/CO 2 ratios (mean: 2.3 ± 1.3). The volcanic CO 2 flux also peaked in November 2015 (mean: 81.3 ± 40.6 kg/s; maximum: 247 kg/s). Using results of magma degassing models and budg…

New evidence for the form and extent of the Pernicana Fault System (Mt. Etna) from structural and soil–gas surveying

A multidisciplinary study based on structural and soil–gas surveys was carried out in order to investigate the relationship between soil CO2 degassing and the tectonic setting of the lower northeastern flank of Mt. Etna volcano. The results show that anomalous soil CO2 emissions occur mainly along faults trending WNW–ESE and also where these faults intersect the other main fault set (trending NE–SW) that displaces the study area. In particular, anomalies in CO2 degassing were revealed both along the Pernicana Fault and along another fault (Fiumefreddo Fault) which may represent the prolongation of the former towards the Ionian Sea coast. In the areas where these structures show evident surf…

Unmanned aerial vehicle measurements of volcanic carbon dioxide fluxes

[i] We report the first measurements of volcanic gases with an unmanned aerial vehicle (UAV). The data were collected at La Fossa crater, Vulcano, Italy, during April 2007, with a helicopter UAV of 3 kg payload, carrying an ultraviolet spectrometer for remotely sensing the SO 2 flux (8.5 Mg d- 1 ), and an infrared spectrometer, and electrochemical sensor assembly for measuring the plume CO 2 /SO 2 ratio; by multiplying these data we compute a CO 2 flux of 170 Mg d -1 . Given the deeper exsolution of carbon dioxide from magma, and its lower solubility in hydro-thermal systems, relative to SO 2 , the ability to remotely measure CO 2 fluxes is significant, with promise to provide more profound…

Diffuse degassing of carbon dioxide at Somma-Vesuvius volcanic complex (Southern Italy) and its relation with regional tectonics

Abstract A systematic survey of soil CO 2 concentrations was carried out on the flanks of Somma–Vesuvius volcano in order to constrain possible pathways responsible of carbon dioxide diffuse degassing taking place during the present state of quiescence. Measurements were performed at 1162 sites in late winter–spring 2000, highlighting that soil CO 2 concentrations range from 50 to 10500 ppmV. A statistical analysis was developed in order to define the threshold value of anomaly and separate the biogenic CO 2 component, produced by soil respiration, from the inorganic component of deep provenance. A computer routine was also elaborated to interpret the grid of CO 2 anomalous concentration va…

Patterns in the recent 2007-2008 activity of Mount Etna volcano investigated by integrated geophysical and geochemical observations

[1] Seismic, deformation, and volcanic gas observations offer independent and complementary information on the activity state and dynamics of quiescent and eruptive volcanoes and thus all contribute to volcanic risk assessment. In spite of their wide use, there have been only a few efforts to systematically integrate and compare the results of these different monitoring techniques. Here we combine seismic (volcanic tremor and long-period seismicity), deformation (GPS), and geochemical (volcanic gas plume CO2/SO2 ratios) measurements in an attempt to interpret trends in the recent (2007–2008) activity of Etna volcano. We show that each eruptive episode occurring at the Southeast Crater (SEC)…

A PTFE membrane for the in situ extraction of dissolved gases in natural waters: Theory and applications

[1] A new method for extracting dissolved gases in natural waters has been developed and tested, both in the laboratory and in the field. The sampling device consists of a polytetrafluroethylene (PTFE) tube (waterproof and gas permeable) sealed at one end and connected to a glass sample holder at the other end. The device is pre-evacuated and subsequently dipped in water, where the dissolved gases permeate through the PTFE tube until the pressure inside the system reaches equilibrium. A theoretical model describing the time variation in partial gas pressure inside a sampling device has been elaborated, combining the mass balance and “Solution-Diffusion Model” (which describes the gas permea…

Fault-controlled Soil CO2 Degassing and Shallow Magma Bodies: Summit and Lower East Rift of Kilauea Volcano (Hawaii), 1997

Soil CO2 flux measurements were carried out along traverses across mapped faults and eruptive fissures on the summit and the lower East Rift Zone of Kilauea volcano. Anomalous levels of soil degassing were found for 44 of the tectonic structures and 47 of the eruptive fissures intercepted by the surveyed profiles. This result contrasts with what was recently observed on Mt. Etna, where most of the surveyed faults were associated with anomalous soil degassing. The difference is probably related to the differences in the state of activity at the time when soil gas measurements were made: Kilauea was erupting, whereas Mt. Etna was quiescent although in a pre-eruptive stage. Unlike Mt. Etna, fl…