Search

In summer 2013 a toxic and polluting gas blowout (19 tonnes day(-1) CO2, 95 kg day(-1) CH4) occurred from two shallow boreholes drilled at only 50 m from the International Airport of Rome (Italy), in the town of Fiumicino. Another gas blowout occurred in the same period from a borehole located offshore, 2 km away, also generating sea-water acidification; it lasted only a couple of days. Onshore, CO2 was also diffusing from holes within the soil, particularly toward the airport, generating a soil flux up to 1.8 tonnes day(-1). In 3.5 months similar to 1500 tonnes of CO2 and 5.4 tonnes of CH4 were emitted in the atmosphere. Temporal monitoring of gas geochemistry indicates that in this area a mixing occurs between shallow and pressurized gas pockets, CO2-dominated, but with different chemical (i.e., He/CH4 ratio) and isotopic (He-3/He-4, delta C-13-delta D-CH4) characteristics. Numerical simulation of CO2 dispersion in the atmosphere showed that dangerous air CO2 concentrations, up to lethal values, were only found near the vents at a height of 0.2 m. Fiumicino is a high blowout risk area, as CO2 rising through deep reaching faults pressurizes the shallow aquifer contained in gravels confined underneath shales of the Tiber delta deposits. The Fiumicino blowout is a typical example of dangerous phenomenon that may occur in urban context lying nearby active or recent volcanoes and requires quick response on hazard assessment by scientists to be addressed to civil protection and administrators.

The main CO2 diffuse degassing structures (DDS) of Stromboli were identified through extensive CO2 soil flux investigations, with 3600 measurements by an accumulation chamber. These DDS extend from the nearby crater area of Pizzo sopra la Fossa (Pizzo) to the coastal area of Pizzillo and are all associated with NE–SW deep fractures, corresponding to the main volcano-tectonic axis of the island, some of which produced flank eruptions in prehistoric times. In each of the four main DDS, a target area was defined covering the zone with the highest CO2 soil flux, where periodic CO2 flux surveys were carried out. The highest CO2 release was observed during the 2007 eruption and high flux values were recorded at both Pizzo and Pizzillo also in moments of high prolonged Strombolian activity (high number of daily explosions observed from the craters and/or high frequency of VLP seismic events). In order to better investigate the rate of diffuse CO2 degassing in relation to volcanic activity, an automatic station hourly measuring CO2 soil flux and environmental parameters (atmospheric T, P and humidity, soil moisture and T, wind speed and direction) was installed in March 2007 at Nel Cannestra and Rina Grande DDS. Unusual positive correlations were found at Nel Cannestra between gas flux and SE wind speed and at Rina Grande between gas flux and soil moisture, which are explained by the local conditions, which favour respectively a Venturi effect and the increase in gas flux toward the station during rains. Ten months of continuous recording confirmed the strong influence of environmental conditions on the CO2 soil flux, but statistical data processing made it possible to recognize clear positive anomalies expressing high rates of deep magmatic CO2 degassing. Comparison with seismic data indicates that high CO2 fluxes are apparently correlated with increases in volcanic activity, such as higher explosion frequency and VLP amplitude. Particularly promising is the temporal coincidence of highest recorded flux anomaly with a major explosion that occurred during the observation period. Data confirm that the two continuously monitored DDS are preferentially deep degassing sites, where anomalous increases of CO2 release could represent a geochemical precursor for either high energy explosions from the craters or the opening of flank eruptive fissures that might threaten the village of Stromboli.

Turrialba volcano lies in the southern sector of the Central American Volcanic Front (CAVF) in Costa Rica. The geochemistry of major and trace elements, and Sr and Nd isotopes of a selected suite of volcanic rocks ranging in composition from basaltic andesite to dacite and belonging to the last 10ka of activity of Turrialba volcano is described, together with the He-, Ne-, and Ar-isotope compositions of fluid inclusions hosted in olivine and pyroxene crystals. Most of the variability in the rock chemistry is consistent with typical trends of fractional crystallization, but there is an outlying group of andesites that displays an adakite-like composition (with a consistent depletion in high-field-strength elements and a marked enrichment in Sr) and low 3He/4He ratios (7.0-7.2 Ra). The trace-element composition of these rocks is typical of subduction-related magmas influenced by an OIB-like component at the source associated with the subduction of the Galapagos seamounts. The 87Sr/86Sr (0.703612-0.703678) and 143Nd/144Nd (0.512960-0.512984) ratios of the bulk rocks vary within narrow ranges, and are among the least-radiogenic isotope signatures of the CAVF volcanoes. The 3He/4He ratios measured in fluid inclusions hosted in olivine crystals (up to 8.1 Ra) are among the highest for the CAVF, and indicate that radiogenic 4He from fluids derived from the subducting slab contribute negligibly to the mantle wedge. The difference in He isotopes between most of studied rocks and those showing adakite-like features reasonably reflects two distinct components in the local mantle: (1) a MORB-like component, characterized by the highest He-isotope ratios (7.8-8.1 Ra), and (2) an OIB-like component, characterized by lower He-isotope ratios (7.0-7.2 Ra), coming from the subduction of the Galapagos seamounts. An overview at the regional scale indicates that high He-isotope ratios are peculiar to the two extreme sectors of the CAVF (Costa Rica to the south and Guatemala to the north), whereas in the central sector (Nicaragua) the magma source is probably contaminated by slab fluids.For the past few years Turrialba volcano has been in a volcanic unrest phase that has included a series of explosions, the most recent of which occurred between October 2014 and May 2015. The volcano is subject to an ongoing safety alert due to the possibility of a magmatic eruption. One of the crucial questions to be addressed is the kind of eruption that can be expected, and hence what type of magma is likely to be involved. The high 3He/4He ratios (7.8-8.0 Ra) measured during 2011 at high-temperature fumaroles of Turrialba craters are comparable to those measured in fluid inclusions of basaltic andesites that erupted in 1864-1866, suggesting that the magma currently feeding the shallow plumbing system has similar geochemical characteristics to the most recently erupted magma.

Soil CO 2 flux and 222 Rn activity measurements may positively contribute to the geochemical monitoring of active volcanoes. The influence of several environmental parameters on the gas signals has been substantially demonstrated. Therefore, the implementation of tools capable of removing (or minimising) the contribution of the atmospheric effects from the acquired time series is a challenge in volcano surveillance. Here, we present 4 years-long continuous monitoring (from April 2007 to September 2011) of radon activity and soil CO 2 flux collected on the NE flank of Stromboli volcano. Both gases record higher emissions during fall–winter (up to 2700 Bq * m − 3 for radon and 750 g m − 2 day − 1 for CO 2 ) than during spring–summer seasons. Short-time variations on 222 Rn activity are modulated by changes in soil humidity (rainfall), and changes in soil CO 2 flux that may be ascribed to variations in wind speed and direction. The spectral analyses reveal diurnal and semi-diurnal cycles on both gases, outlining that atmospheric variations are capable to modify the gas release rate from the soil. The long-term soil CO 2 flux shows a slow decreasing trend, not visible in 222 Rn activity, suggesting a possible difference in the source depth of the of the gases, CO 2 being deeper and likely related to degassing at depth of the magma batch involved in the February–April 2007 effusive eruption. To minimise the effect of the environmental parameters on the 222 Rn concentrations and soil CO 2 fluxes, two different statistical treatments were applied: the Multiple Linear Regression (MLR) and the Principal Component Regression (PCR). These approaches allow to quantify the weight of each environmental factor on the two gas species and show a strong influence of some parameters on the gas transfer processes through soils. The residual values of radon and CO 2 flux, i.e. the values obtained after correction for the environmental influence, were then compared with the eruptive episodes that occurred at Stromboli during the analysed time span (2007–2011) but no clear correlations emerge between soil gas release and volcanic activity. This is probably due to i ) the distal location of the monitoring stations with respect to the active craters and to ii ) the fact that during the investigated period no major eruptive phenomena (paroxysmal explosion, flank eruption) occurred. Comparison of MLR and PCR methods in time-series analysis indicates that MLR can be more easily applied to real time data processing in monitoring of open conduit active volcanoes (like Stromboli) where the transition to an eruptive phase may occur in relatively short times.

A borehole drilled at Fiumicino (Rome) down to only 27 m depth in a zone where no gas emission at the surface was known, caused a gas blowout from a pressurized gas pocket confined beneath a clay cover. Gas slowly diffused from the borehole within superficial permeable sand. Seven persons living in three ground floor flats of a near building had to be hospitalized due to CO2 exposure. All the houses in the proximity were evacuated. At the request of the Fire Brigade two additional boreholes were drilled nearby, hoping that this could rapidly exhaust the gas stored underground. To the contrary the soil gas flux near houses increased and indoor CO2 air concentration rapidly rose to lethal values (15 to 30 vol.%). As a remediation we suggested to restore the continuity of the impervious gas cover by squeezing quick-setting cement into the formation through new boreholes to be drilled near the existing ones. Although the first cement squeeze reduced drastically the CO2 soil flux and indoor concentration, six additional squeezes had to be carried out in order to lower the gas emission below the gas hazard threshold. The gas was mostly made of CO2 (98 vol.%) with minor N2 and CH4. Its chemical and isotopic composition (δ13CCO2 = − 1.55; 3He/4He = 0.314 Ra) is similar to that of the gas manifestations of Mts. Sabatini and Alban Hills volcanic areas. Though being somewhat contaminated by crustal and shallow organic volatiles, these gases likely have a component originated in the mantle, that beneath the volcanic Roman Comagmatic Province is probably deeply contaminated with crustal material. The Fiumicino gas blowout indicates that the area of Central Italy characterized by strong CO2 degassing extends westerly to include the Tyrrhenian coast.

Significant changes in the helium and carbon isotopic composition of shallow thermal waters vs. gas and a crater fumarolic gas have been recorded at Stromboli prior and during the 2002–2003 eruption. The3He/4He ratios corrected for air contamination (Rc/Ra), and δ13C of fumarolic gases gradually increased from May to November 2002 before the eruption onset. These variations imply early degassing of a gas-rich magma at depth that likely fed both the intense Strombolian activity and small lava overflows recorded during that period. The lava effusion of late December 2002 was shortly preceded by a marked Rc/Ra decrease both in water and fumarolic gases. Comparison of He/CO2 and CH4/CO2 ratios in dissolved gas and with\({\rm \delta }^{13} {\rm C}_{{\rm CO}_2 }\) values rules out the Rc/Ra decrease due to an increasing input of radiogenic4He. The Rc/Ra decrease is attributed to the He isotope fractionation during rapid magma ascent and degassing. A new uprising of 3He-rich magma probably occurred in January to February 2003, when Rc/Ra ratios displayed the highest values in dissolved gases ever measured before (4.56 Rc/Ra). The increase in He/CO2 and CH4/CO2 ratios and decrease in δ13C of dissolved CO2 was recorded after the 5 April 2003 explosive paroxysm, likely caused by enhanced gas-water interaction inducing CO2 dissolution. No anomalous Rc/Ra values were recorded in the same period, when usual Strombolian activity gradually resumed.

Significant changes in both the chemistry of coastal thermal waters and the soil CO 2 and Rn emissions in the crater area were recorded at Stromboli prior to the eruption that began on 28 December 2002. The dissolved CO 2 contents and the δ 13 C and 3 He/ 4 He values were elevated in the thermal aquifer from July 2002. Synchronous variations in the same isotope ratios were recorded in the summit fumarolic gases, with both 3 He/ 4 He and δ 13 C values of gases released from a fumarole in the summit area increasing between May and November 2002. These variations are indicative of early degassing of a new gas-rich magma batch with a 13 C- and 3 He-rich signature. This magma recharge probably fed the intense Strombolian activity recorded during that period. The eruption began with a major explosion that produced a glowing avalanche, immediately followed by a fluid lava overflow from the NE crater and subsequent lava effusion from vents opened in the Sciara del Fuoco depression. Sharp increases in CO 2 soil flux and Rn emissions― to values never observed previously―were recorded in the summit crater area 10 d before the eruption onset. These CO 2 and Rn anomalies are indicative of a high gas-driven magma supply rate and gas overpressure within the conduit. The sudden depressurization of the magma filling the upper conduit probably caused the major explosion that occurred on 28 December, which heralded the effusive phase. These data demonstrate the importance of collecting a wide spectrum of geochemical data from different geological sites when monitoring a volcano.

""\\"\\\\\\"Platanares and Azacualpa geothermal sites of Honduras are located in an inner part of the Caribbean Plate far from the active volcanic front of Central America. Here geology indicates that there are not the conditions for the occurrence of shallow magmatic heat sources for high-enthalpy geothermal resources. Geothermal perspectives are related to the possibility of a deep circulation of meteoric water along faults and the storage of the heated fluid in fractured permeable reservoirs. Geochemical geothermometers indicate a temperature for the deeper part of the geothermal reservoir close to 200 °C for Platanares and of 150–170 °C for Azacualpa. Calcite scaling, with subordinate silica deposition has to be expected in both sites. CO2 soil flux investigations have been carried out in both areas and reveal the presence of positive anomalies likely corresponding to the presence at depth of fractured degassing geothermal reservoirs. Compared with the geothermal areas of Central Italy whose reservoirs are hosted in carbonate rocks, e.g. Latera (Chiodini et al., 2007), the CO2 soil flux measured in Honduras is significantly lower (mean of 17 g\\\\\\\\\\\\\\\/m2day at Platanares and of 163 g\\\\\\\\\\\\\\\/m2day at Azacualpa) probably because of the dominant silicate nature of the deep reservoirs.\\\\\\"\\"""

Gas hazard was evaluated in the three most important cold gas emission zones on the flanks of the quiescent Colli Albani volcano. These zones are located above structural highs of the buried carbonate basement which represents the main regional aquifer and the main reservoir for gas rising from depth. All extensional faults affecting the limestone reservoir represent leaking pathways along which gas rises to the surface and locally accumulates in shallow permeable horizons forming pressurized pockets that may produce gas blowout when reached by wells. The gas, mainly composed of CO 2 (>90 vol.%), contains appreciable quantities of H 2 S (0.35–6 vol.%), and both represent a potentially high local hazard. Both gases are denser than air and accumulate near ground where they may reach hazardous concentrations, and lethal accidents frequently occur to animals watering at local ponds. In order to evaluate the rate of degassing and the related hazard, CO 2 and H 2 S diffuse soil flux surveys have been repeatedly carried out using an accumulation chamber. The viscous gas flux of some important discrete emissions has been evaluated and the CO 2 and H 2 S air concentration measured by portable devices and by Tunable Diode Laser profiles. The minimum potential lethal concentration of the two gases (250 ppm for H 2 S and 8 vol.% for CO 2 ) is 320 times higher for CO 2 , whereas the CO 2 /H 2 S concentration ratio in the emitted natural gas is significantly lower (15–159). This explains why H 2 S reaches hazardous, even lethal, concentrations more frequently than CO 2 . A relevant hazard exists for both gases in the depressed zones (channels, excavations) particularly in the non-windy early hours of the day.

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.

The Albano Lake is the deepest volcanic lake in Italy (− 167 m) and fills the youngest maar of the quiescent Colli Albani volcano. The lake has undergone significant level changes and lahar generating overflows occurred about 5800 yrs B.P. and likely in 398 b.C., when Romans excavated a tunnel drain through the maar wall. Hazardous lake rollovers and CO 2 release are still possible because the Albano volcano shows active ground deformation, gas emission and periodic seismic swarms. On November 2005, the first high resolution bathymetric survey of the Albano Lake was performed. Here we present the results provided by a Digital Elevation Model and 2-D and 3-D images of the crater lake floor, which is made by coalescent and partly overlapping craters and wide flat surfaces separated by some evident scarps. Submerged shorelines are identified at depths between − 20 m and − 41 m and indicate the occurrence of significant lake level changes, likely between 7.1 and 4.1 ka. The current lake volume is ~ 447.5 × 10 6 m 3 and the total quantity of dissolved CO 2 is 6850 t estimated by chemical analyses of samples collected on May 2006. A decrease of nearly one order of magnitude of the CO 2 dissolved in the lake water below − 120 m, observed from December 1997 to May 2006 (from 4190 to 465 t respectively), has been attributed to lake water overturn. The observed oscillations of the dissolved CO 2 concentrations justify the efforts of monitoring the chemical and physical characteristics of the lake. At present the quantity of dissolved CO 2 is very far from saturation and Nyos-type events cannot presently occur.

Lake Albano, located 20 km to the SE of Rome, is hosted within the most recent crater of the quiescent Alban Hills volcanic complex that produced hydromagmatic eruptions in Holocene times. Stratigraphic, archaeological and historical evidence indicates that the lake level underwent important variations in the Bronze Age. Before the IV century B.C. several lahars were generated by water overflows from the lake and in the IV century B.C. Romans excavated a drainage tunnel. The lake is located above a buried carbonate horst that contains a pressurized medium-enthalpy geothermal reservoir from which fluids escape to the surface to produce many important gas manifestations of mostly CO2. Previous studies recognized the presence of gas emissions also from the crater bottom. In 1997 the possibility of a Nyos-type event triggered by a lake rollover was considered very low, because the CO2 water concentration at depth was found to be far from saturation. However, considering the high population density nearby, the Italian Civil Protection Department recommended that periodical monitoring be carried out. To this scope we initiated in 2001 a systematic geochemical study of the lake. Thirteen vertical profiles have been repeatedly carried out in 2001–2006, especially in the deepest part of the lake (167 m in 2006), measuring T, pH, dissolved O2 and electrical conductivity. Water samples were collected from various depths and chemically and isotopically analysed. Two similar profiles have been measured also in the nearby Nemi crater lake. Results indicate that in the 4.5 years of monitoring the pressure of gas dissolved in the Lake Albano deep waters remained much lower than the hydrostatic pressure. A CO2 soil survey carried out on the borders of the two lakes, indicates the presence of some zones of anomalous degassing of likely magmatic origin. A water overturn or a heavy mixing of deep and shallow waters likely occurred in winter 2003–2004, when cold rainfall cooled the surface water below 8.5 °C. Such overturns cause only a limited gas exsolution from the lake when the deep water is brought to a few meters depth but can explain the observed decrease with time of dissolved CO2 at depth and related water pH increase. A gas hazard could occur in the case of a sudden injection through the lake bottom of a huge quantity of CO2-rich fluids, which might be caused by earthquake induced fracturing of the rock pile beneath the lake. A limnic gas eruption might also occur should CO2 concentration build up within the lake for a long time.

In order to test the potentiality of soil CO2 diffuse degassing measurements for the study of underground mass and heat transfer in geothermal systems detailed surveys were performed at Latera caldera, which is an excellent test site, because of the abundant available subsurface data. Over 2500 measurements of soil CO2 flux revealed that endogenous CO2 at Latera caldera concentrates on a NE-SW band coinciding with a structural high of fractured Mesozoic limestones hosting a water-dominated high-enthalpy geothermal reservoir. The total hydrothermal CO2 degassing from the structural high has been evaluated at 350 t d-1 from an area of 3.1 km2. It has been estimated that such a CO2 release would imply a geothermal liquid flux of 263 kg s-1, with a heat release of 239 MW. The chemical and isotopic composition of the gas indicates a provenance from the geothermal reservoir and that CO2 is partly originated by thermal metamorphic decarbonation in the hottest deepest parts of the system and partly has a likely mantle origin. The ratios of CO2, H2, CH4, and CO to Ar were used to estimate the T-P conditions of the reservoir. Results cluster at T ∼ 200-300°C and PCO2 ∼ 100-200 bars, close to the actual well measurements. Finally, the approach proved to be an excellent tool to investigate the presence of an active geothermal reservoir at depth and that the H2-CO2- CH4-CO-Ar gas composition is a useful T-P geochemical indicator for such CO2 rich geothermal systems.

[1] The peculiarity of the quiescent La Fossa volcano is the occurrence of “crises” characterized by strong increases of fumarole T and output and by chemical changes indicative of an increasing input of magmatic fluids. Several surveys carried out during a new “crisis” began in November 2004 indicate that the total diffuse CO2 emission for the crater area increases by one order of magnitude during crises (up to 1600 ton·d−1 in December 2005). Concern exists on the possibility that these crises be related to an unrest process leading to eruption. The repetition along decades of the same gas compositional variations during crises, their temporal coincidence with increases of the local shallow seismicity, and the lack of any significant ground motion, rather suggest that they correspond to moments of increasing volatile release from a stationary magma system.