Diffuse emission of CO2 from the Fossa crater,Vulcano Island (Italy)

 Numerous measurements of CO₂ degassing from the soil, carried out with the accumulation chamber method, indicate that in the period April–July 1995 the upper part of the Fossa cone released a total output of 200 t d^–1 of CO₂, which corresponds to approximately 1000 t d^–1 of steam. These large amounts of fluids are of the same order of magnitude as those released by the high temperature fumarolic field located inside the crater. The spatial distribution of soil gas fluxes shows that the main structures releasing CO₂ are the inner slopes of the crater and a NW–SE line, located NE of the crater rim, which correspond to the main direction of Vulcano Island active faults. The comparison of the φCO₂ maps with the soil temperature distribution, derived from both direct measurements and airborne infrared images, indicates the occurrence of extensive condensation of fumarolic steam within the upper part of the Fossa cone, whose total amount is comparable to the rainfall budget. Part of the condensate which originates from this process contributes to the recharge of the phreatic aquifer of Porto Plain, modifying the chemical and isotopic composition of the groundwater. Received: 1 September 1995 / Accepted: 8 January 1996     

Evolution of Br/Cl ratios in fumarolic salammoniac from Vulcano (Aeolian Islands,Italy)

 Bromine/chlorine ratios in salammoniac samples, collected from 1983 to 1994 at the Fossa crater fumaroles of Vulcano (Aeolian Islands), were determined. The data obtained in this work have been compared to those obtained by Coradossi et al. (1985) in order to carry out a systematic study of the Br/Cl ratio variations since 1977. Br/Cl ratios range from 0.04 to 0.29. The Br/Cl ratio variations observed have been interpreted as the result of different contributions among deep and shallow components feeding the fumarolic fluids of Vulcano. The Br/Cl increases, which occurred from 1977 to 1979, in 1983–1984 and in 1992–1993, have been connected to an increased input of magmatic gases. Received: 10 November 1995 / Accepted: 12 July 1996     

Evolution of fumarolic gases — boundary conditions set by measured parameters: case study at Vulcano,Italy

Physical, chemical and isotopic parameters were measured in fumaroles at the Vulcano crater and in drowned fumaroles near the beach. The data were used to define boundary conditions for possible conceptual models of the system.Crater fumaroles: time variations of CO₂ and SO₂ concentrations indicate mixing of saline gas-rich water with local fresh water. Cl/Br ratios of 300– 400 favour sea-water as a major source for Cl, Brand part of the water in the fumaroles. Cl concentrations and D values revealed, independently, amixing of 0.75 sea-water with 0.25 local freshwaterin furmarole F-5 during September 1982.Patterns of parameter correlation and mass balances reveal that CO₂, S, NH₃ and B originate from sources other than sea water. The CO₂ value of ¹³C = – 2%_o favours, at least partial, origin from decomposition of sedimentary rocks rather than mantle-derived material. Radiogenic⁴He(1.3 × lO^–3 ccSTP/g water) and radiogenic⁴⁰Ar(10.6 × 10^–4 ccSTP/g water) are observed, (⁴He/⁴⁰Ar)_radiogenic = 1.2, well in the range of values observed in geothermal systems.Drowned fumaroles: strongly bubbling gas at a pond and at the beachappears to have the same origin and initial compositionas the crater fumaroles (2 km away). The fumarolic gas is modified by depletion of the reactive gases, caused by dissolution in shallow-water. Atmospheric Ne, Ar, Kr and Xe are addeden route, some radiogenic He and Ar are maintained. The Vulcano system seems to be strongly influenced by the contribution of sea-water and decomposition of sedimentary rocks. Evidence of magmatic contributions is mainly derived from heat.     

Helium isotopic ratio in Vulcano island fumaroles: temporal variations in shallow level mixing and deep magmatic supply

Intensive gas emanations occur throughout the island of Vulcano, Italy. Sharp fluctuations recorded in the crater gas composition suggest the presence of two separate volcanic reservoirs and continuous mixing with another source, “crustal” waters. This mixing differs between the beach and crater fumaroles. Gas samples from three crater fumaroles with temperatures ranging from 200 to 550 ° C were sampled repeatedly over a one year period. During the same interval of time, six samples from submarine and subaerial beach fumaroles and water well gases were also sampled. Gases from one crater fumarole (F5) showed variations of (³He/⁴He)_fumarole to (³He/⁴He)_air between 5 and 6 correlated with variations of several chemical species. High ³He/⁴He ratios for the beach fluids, similar to those of crater fluids, suggest the existence of a unique large magmatic reservoir at depth feeding both the crater and beach intermediate reservoirs. However, temporal changes clearly indicate variable degrees of fluids mixing, and the geographic distribution of the ³He/⁴He ratios as well as the chemical composition of the fluids suggest the existence between the magma reservoir and the surface of two intermediate different reservoirs, independently related to crater and to beach fumaroles.     

Variations in surface manifestations at vulcano (Aeolian Islands,Italy) as a possible evidence of deep processes

Five years of geochemical surveillance at Vulcano have shown interesting changes in the physico-chemical characters of the fumaroles at the crater and of the phreatic waters in the surrounding area. In particular, 1) The maximum temperature of the fumaroles, which had been of about 200°C for at least 30 years, rose suddenly to above 300°C: after a period of rather constant values, a decreasing trend has recently been observed; 2) An increase of CO₂, S compounds and HF with respect to HCl, B, Br occurred in the gas composition contemporaneous to the rise in temperature. This increase is now gradually declining; 3) Higher concentrations of sulphate ion and silica in phreatic waters accompanied the thermal changes observed at the fumaroles. According to a model previously proposed (Martini et al., 1980), the increase in the above mentioned factors would reflect an increasing magmatic contribution to the volcanic system, which might be due to an increased permeability to fluids at depth. Because a sensible seismic shock occurred in the area a few months after the first chemical and thermal variations had been observed, such variations may be regarded as forerunners of the seismic event, and may be used to forecast some months in advance changes occurring at depth. The work was carried out within the research programme of C.N.R. Centro di Studio per la Mineralogia e la Geochimica dei Sedimenti, Florence, Italy.     

Guagua pichincha volcano, Ecuador: fluid geochemistry in volcanic surveillance

The densely populated metropolitan area of Quito is located on the slopes of the active Guagua Pichincha volcano at only 10 km from the crater. Recently, the Italian Ministry of Foreign Affairs sponsored a project for the mitigation of volcanic hazard in this area. The geochemical study carried out as part of this project was aimed at constructing a geochemical model of the zone for use in volcanic surveillance.According to this geochemical model, a hydrothermal aquifer (T = 200–240°C), fed both by meteoric waters and by fluids released by a magma body, lies at shallow levels beneath Guagua Pichincha crater. The crater fumaroles are essentially fed by steam boiled off from the hydrothermal aquifer. The high flow rate fumaroles located in the dome area show significant SO₂ contents, which suggest a relatively high contribution of magmatic fluids in the zone of the aquifer feeding them. The absence of SO₂ in the fumarolic discharges near the southern crater wall indicates instead that the magmatic fluids dissolve entirely into the aquifer here. The hot springs located at the western end of the crater represent the lateral discharge of the hydrothermal aquifer.On the basis of this model, it is likely that an increment in the flux of both the magmatic fluids and the heat from a magma body produces an increase, albeit small, of the pressure-temperature conditions of the hydrothermal system and consequent changes in flow rate and fluid chemistry of the fumarolic vents. In particular, total sulphur and possibly hydrochloric acid may increase in all the vents and sulphur dioxide may appear in other fumarolic discharges. The varying thermodynamic conditions in the hydrothermal aquifer can be evaluated on the basis of the equilibria among carbon species and hydrogen. Only minor delayed changes are expected in the physical-chemical characteristics of the springs located at the western end of the crater.     

Magma-hydrothermal system interaction inferred from volcanic gas measurements obtained during 2003–2008 at Meakandake volcano,Hokkaido, Japan

Phreatic eruptions occurred at the Meakandake volcano in 1988, 1996, 1998, 2006, and 2008. We conducted geochemical surveillance that included measurements of temperature, SO₂ emission rates, and volcanic gas composition from 2003 to 2008 at the Nakamachineshiri (NM), Northwest (NW), and Akanuma (AK) fumarolic areas, and the 96–1 vent, where historical eruptions had occurred. The elemental compositions of the gases discharged from the different areas are similar compared with the large variations observed in volcanic gases discharged from subduction zones. All the gases showed high apparent equilibrium temperatures, suggesting that all these gases originated from a common magmatic gas. The gases discharged from each area also exhibited different characteristics, which are probably the results of differences in the conditions of meteoric water mixing, quenching of chemical reactions, and vapor-liquid separation. The highest apparent equilibrium temperatures (about 500°C) were observed in the case of NW fumarolic gases, despite the low outlet temperature of about 100°C at these fumaroles. Since the NW fumaroles were formed as a result of the 2006 phreatic eruption, the high-temperature gas supply to the NW fumarole suggests that the phreatic eruption was caused by the ascent of high-temperature magmatic gases. The temperatures, compositions, and emission rates of the NM and 96–1 gases did not show any appreciable change after the 2006 eruption, indicating that each fumarolic system had a separate magmatic-hydrothermal system. The temperatures, compositions, and emission rates of the NM fumarolic gases were apparently constant, and these fumaroles are inferred to be formed by the evaporation of a hydrothermal system with a constant temperature of about 300°C. The 96–1 gas compositions showed large changes during continuous temperature decrease from 390° to 190°C occurred from 2003 to 2008, but the sulfur gas emission rates were almost constant at about four tons/day. At the 96–1 vent, the SO₂/H₂S ratio decreased, while the H₂/H₂O ratio remained almost constant; this was probably caused by the rock-buffer controlled chemical reaction during the temperature decrease.     

Chemical evolution and volcanic activity of the active crater lake of Poás volcano, Costa Rica, 1993–1997

Concentrations of chloride and sulfate and pH in the hot crater lake (Laguna Caliente) at Poás volcano and in acid rain varied over the period 1993–1997. These parameters are related to changes in lake volume and temperature, and changes in summit seismicity and fumarole activity beneath the active crater. During this period, lake level increased from near zero to its highest level since 1953, lake temperature declined from a maximum value of 70°C to a minimum value of 25°C, and pH of the lake water increased from near zero to 1.8. In May 1993 when the lake was nearly dry, chloride and sulfate concentrations in the lake water reached 85,400 and 91,000 mg l⁻¹, respectively. Minimum concentrations of chloride and sulfate after the lake refilled to its maximum volume were 2630 and 4060 mg l⁻¹, respectively. Between January 1993 and May 1995, most fumarolic activity was focused through the bottom of the lake. After May 1995, fumarolic discharge through the bottom of the lake declined and reappeared outside the lake within the main crater area. The appearance of new fumaroles on the composite pyroclastic cone coincided with a dramatic decrease in type B seismicity after January 1996. Between May 1995 and December 1997, enhanced periods of type A seismicity and episodes of harmonic tremor were associated with an increase in the number of fumaroles and the intensity of degassing on the composite pyroclastic cone adjacent to the crater lake. Increases in summit seismic activity (type A, B and harmonic tremor) and in the height of eruption plumes through the lake bottom are associated with a period of enhanced volcanic activity during April–September 1994. At this time, visual observations and remote fumarole temperature measurements suggest an increase in the flux of heat and gases discharged through the bottom of the crater lake, possibly related to renewed magma ascent beneath the active crater. A similar period of enhanced seismic activity that occurred between August 1995 and January 1996, apparently caused fracturing of sealed fumarole conduits beneath the composite pyroclastic cone allowing the focus of fumarolic degassing to migrate from beneath the lake back to the 1953–1955 cone. Changes in the chemistry of summit acid rain are correlated changes in volcanic activity regardless of whether fumaroles are discharging into the lake or are discharging directly into the atmosphere.     

Genesis and evolution of the fumaroles of vulcano (Aeolian Islands,Italy): a geochemical model

A geochemical model explaining the presence of fumaroles having different gas composition and temperature at the top of the crater and along the northeastern coast of Vulcano island is proposed. A pressurized biphase (liquid-vapor) reservoir at the depth of about 2 km is hypothesized. Energy and mass balance sheets controlP-T conditions in the system.P-T must vary along a boiling curve of brine as liquid is present. The CO₂ content in the steam is governed by the thermodynamic properties of the fluids in the H₂-NaCl-CO₂ system. On the assumption that oxygen fugacity in the system is between the HM-FMQ oxygen buffers, observed SO₂/H₂S, CO₂/CO, CO/CH₄ ratios in the fumarolic gases at the Fossa crater appear in equilibrium with a temperature higher than that observed, such as may exist at depth. The more reduced gas phases present on the sea-side may result from re-equilibrium processes in shallower aquifers. The suggested model would help in monitoring changes in volcanic activity by analyzing fumarolic gases.     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Presence of native gold and tellurium in the active high-sulfidation hydrothermal system of the La Fossa volcano (Vulcano, Italy)

Grains of native gold and tellurium were found in siliceous hydrothermally altered rocks in the high-temperature (170–540°C) fumarolic field of the La Fossa volcano (Island of Vulcano). In addition to Au and Te, Pb–Bi sulfides (cannizzarite) and Tl-bromide chloride were found as sublimates in the hottest fumarolic vents of the crater rim. The chemical composition of altered rocks associated with sublimate deposition indicate the presence of a significant concentration of Te (up to 75 ppm), while gold concentrations are very low (<9 ppb). Pb, Bi and Tl are strongly enriched in the hottest and less oxidized fumarolic vents, reaching concentrations of 2186, 146 and 282 ppm, respectively. These elements are transported (generally as chloride complexes) to the surface by volcanic gases, and several of these (Bi, Te, Tl) are originated from magma degassing. The silicic alteration is produced by the flow of fluids with pH<2. High acidity results from introduction of magmatic gases such as SO₂, HCl and HF released by the shallow magmatic reservoir of La Fossa volcano. The silicic alteration found at Vulcano may represent an early stage of the `vuggy silica' facies which characterizes the high-sulfidation epithermal ore deposits, confirming the analogies existing between this type of ore deposit and magmatic-hydrothermal systems associated with island-arc volcanoes.     

The determination of deep temperatures by means of the CO-CO2-H2-H2O geothermometer: an example using fumaroles in the Campi Flegrei,Italy

Chromatographic analyses of fumarolic gases, collected in sampling bottles containing an alkaline solution, have been carried out using a thermal conductivity detector and a flame ionization detector, after catalytic conversion of CO and CH₄. The latter method enables the concentration of carbon monoxide to be measured with sufficient accuracy for use in a CO-CO₂-H₂-H₂O geothermometer. Application of this geothermometer to fumaroles in the crater of Solfatara in the Campi Flegrei, Italy, indicates that they are fed from a steam reservoir at 250±15 °C and at 10^–36±2atm of oxygen. On the other hand, the CH₄-CO₂-H₂-H₂O geothermobarometer seems to re-equilibrate at superficial temperatures and cannot be used for infering thermodynamic conditions at depth. Regular sampling of these fumaroles together with a geothermometric interpretation of the gas analyses provides a means of monitoring, with comparative accuracy, the chemical and thermal evolution of the hydrothermal reservoir below the Solfatara crater. Such monitoring would probably detect an increase in temperature at depth and the injection of magmatic gas into the reservoir.     

Using Crater Lake chemistry to predict volcanic activity at Poás Volcano,Costa Rica

Monitoring of crater lake chemistry during the recent decline and disappearance of the crater lake of Poás Volcano revealed that large variations in SO₄/Cl, F/Cl, and Mg/Cl ratios were caused by the enhanced release of HCl vapor from the lake surface due to increasing lake temperature and solution acidity. Variation in the concentration of polythionic acids (H₂S_xO₆, x=4–6) was the most reliable predictor of renewed phreatic eruptive activity at the volcano, exhibiting sharp decreases three months prior to the initiation of phreatic eruptions in June 1987. Polythionic acids may offer a direct indicator of changing subsurface magmatic activity whereas chloride-based element ratios may be influenced by surface volatilization of HCl and subsequent recycling of acidic fluids in crater lake volcanoes.     

Signs of potential renewal of eruptive activity at La Fossa (Vulcano,Aeolian Islands)

Since the end of the last magmatic eruption (1890), activity of La Fossa (southern Tyrrhenian Sea, Italy) has consisted of fumarolic emissions of fluctuating intensity. Fluids are discharged principally at two fumarolic fields located in the northern rim of the active crater and at the beach sited at its northern foot. Increased thermal, seismic and geochemical activity has been recorded since 1978, when an earthquake of M=5.5 occurred in the region. This paper combines available geophysical and geochemical information in order to develop a tentative interpretation of two episodes of apparent unrest which occurred in 1985 and 1987–1988, enhancing the risk of renewal of the eruptive activity. The 1985 unrest consisted essentially of a sharp build up of the internal pressure in the shallow hydrothermal system, which was induced by the injection of hot gases of magmatic origin. The crater fumaroles displayed significant increases in CO₂ and other acid species, but their outlet temperature did not change. Conversely, the 1987–1988 episode was characterized by appreciable modifications at the crater fumaroles, with only secondary effects at the fumarole system of the beach. The sliding of part of the eastern flank of the La Fossa cone into the sea occurred on 20 April 1988, when the region was affected by crustal dilatation producing a seismic sequence of relatively high intensity. Both episodes of unrest were accompanied by increases of local microseismic activity, which affected the nothern sector of the island in 1985, and the southern one in 1988. Finally, a phase of appreciable areal contraction was detected in 1990, probably due to the effect of the cooling and crystallization of magma at relatively shallow depths, accompanying the increased thermal activity at the crater fumaroles. Regional tectonic stress seems to play an important role in the transition of the volcanic system from a phase of relative stability to a phase of apparent unrest, inducing the heating and the expansion of shallow hydrothermal fluids. Available information is insufficient to indicate whether or not the volcano is building towards the renewal of a magmatic eruption, and there is no evidence to hypothesize episodes of significant magma migration. The frequency of measurements of many parameters needs to be increased in order to learn more about the temporal relationships between geochemical and geophysical variations preceding and accompanying periods of increased thermal activity. This will probably be a valid tool for recognizing short-term precursors of a future eruption, reducing the risk of false alarms.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Volcanic steam output directly measured in fumaroles: the observed variations at Vulcano Island,Italy, between 1983 and 1987

The mass of steam emitted by the fumaroles of the crater of Vulcano (Aeolian Islands, Italy) was evaluated by using a direct measuring method. Measurements were effected with this method between 1983 and 1987 in nine field campaigns, the results of which are given in this paper. The steam flux measurements were performed by an instrument expressly designed for steam condensation. The estimates of the thermal energy transported daily by the steam gave values of up to 10E12 J. The sharp variations in the total mass outputs recorded in 1984 and 1985 are here interpreted as being a consequence of the probable accumulation of fluid pressure at depth, during the evolution of volcanic activity. The different results obtained from the various areas of the fumarolic field during the evolutionary phases have led to the hypothesis that different subsystems exist that feed the fumaroles, and that their activity is triggered by volcano-tectonics. This method can be applied in the evaluation of both fumarolic steam and thermal energy outputs, and therefore it is particularly useful in geothermal exploration, in the evaluation of the environmental impact of volcanic degassing, and in the forecasting of volcanic eruptions. The evaluation of the steam output is also useful for quantifying the release of other gaseous species and giving univocal interpretations regarding their variations in concentrations. Furthermore this direct method provides a new way of calibrating the flux estimates effected by other telemetric techniques (Lidar, Cospec, etc.).     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Temporal variations of gas compositions of fumaroles in the Tatun Volcano Group,northern Taiwan

Hydrothermal activity is common in the Tatun Volcano Group of northern Taiwan. Helium isotopic compositions of fumarolic samples show that mantle component occupies more than 60% in the previous study. Along with recent seismic results, a magma reservoir is inferred to have existed beneath the area of Da-you-keng, where fumarolic venting is the most active in Tatun Volcano Group. Progressive increases of HCl concentrations and SO₂/H₂S ratio in fumaroles from Da-you-keng have been observed since August 2004. The HCl concentration changed from almost the detection limit to thousands of ppm, even up to 30,000 ppm. SO₂/H₂S ratios varied from almost 0 to 3; hence SO₂ became the dominated S species in this area. These variations were accompanied by rising temperature of fumaroles in the Tatun Volcano Group, especially in the area of Da-you-keng (from boiling point to 131 °C). Meanwhile, ³He/⁴He ratios showed a decreasing trend but returned to normal values shortly thereafter. We propose two possible processes, 1) new magma supply and 2) recent opening of fractures in local area, to explain these observations. Based on the change of ³He/⁴He ratio and lack of ground deformation, we consider the latter might be more plausible.     

Helium isotopes in some historical lavas from Mount Vesuvius

³He/⁴He ratios in lavas erupted during the last 360 years at Mt. Vesuvius are between 2.2 and 2.7 R_A (R_A = atmospheric ratio of 1.39 × 10⁻⁶), and are among the lowest values measured in young volcanic rocks. They are also identical to values measured in summit crater fumaroles sampled during 1987–1991. This agreement indicates that the ³He/⁴He ratio in the crater fumaroles faithfully tracks the magmatic value. The relatively low and uniform ³He/⁴He ratio in the lavas reflects either a mantle source enriched in (U + Th)/³He, or a mixture of magmatic and crustal components.     

Geochemistry of volcanic and hydrothermal gases of Mutnovsky volcano,Kamchatka: evidence for mantle,slab and atmosphere contributions to fluids of a typical arc volcano

We report chemical compositions (major and trace components including light hydrocarbons), hydrogen, oxygen, helium and nitrogen isotope ratios of volcanic and geothermal fluids of Mutnovsky volcano, Kamchatka. Several aspects of the geochemistry of fluids are discussed: chemical equilibria, mixing of fluids from different sources, evaluation of the parent magmatic gas composition and contributions to magmatic vapors of fluids from different reservoirs of the Kamchatkan subduction zone. Among reactive species, hydrogen and carbon monoxide in volcanic vapors are chemically equilibrated at temperatures >300°C with the SO₂-H₂S redox-pair. A metastable equilibrium between saturated and unsaturated light hydrocarbons is attained at close to discharge temperatures. Methane is disequilibrated. Three different sources of fluids from three fumarolic fields in the Mutnovsky craters can be distinguished: (1) magmatic gas from a large convecting magma body discharging through Active Funnel, a young crater with the hottest fumaroles (up to 620°C) contributing ~80% to the total volcanic gas output; (2) volcanic fluid from a separate shallow magma body beneath the Bottom Field of the main crater (96–280°C fumaroles); and (3) hydrothermal fluid with a high relative and absolute concentrations of CH₄ from the Upper Field in the main crater (96–285°C fumaroles). The composition of the parent magmatic gas is estimated using water isotopes and correlations between He and other components in the Active Funnel gases. The He-Ar-N₂ systematics of volcanic and hydrothermal fluids of Mutnovsky are consistent with a large slab-derived sedimentary nitrogen input for the nitrogen inventory, and we calculate that only ~1% of the magmatic N₂ has a mantle origin and <<1% is derived from the arc crust.