Diffuse CO<Subscript>2</Subscript> degassing at Vesuvio,Italy

At Vesuvio, a significant fraction of the rising hydrothermal–volcanic fluids is subjected to a condensation and separation process producing a CO₂–rich gas phase, mainly expulsed through soil diffuse degassing from well defined areas called diffuse degassing structures (DDS), and a liquid phase that flows towards the outer part of the volcanic cone. A large amount of thermal energy is associated with the steam condensation process and subsequent cooling of the liquid phase. The total amount of volcanic–hydrothermal CO₂ discharged through diffuse degassing has been computed through a sequential Gaussian simulation (sGs) approach based on several hundred accumulation chamber measurements and, at the time of the survey, amounted to 151 t d^–1. The steam associated with the CO₂ output, computed assuming that the original H₂O/CO₂ ratio of hydrothermal fluids is preserved in fumarolic effluents, is 553 t d^–1, and the energy produced by the steam condensation and cooling of the liquid phase is 1.47×10¹² J d^–1 (17 MW). The location of the CO₂ and temperature anomalies show that most of the gas is discharged from the inner part of the crater and suggests that crater morphology and local stratigraphy exert strong control on CO₂ degassing and subsurface steam condensation. The amounts of gas and energy released by Vesuvio are comparable to those released by other volcanic degassing areas of the world and their estimates, through periodic surveys of soil CO₂ flux, can constitute a useful tool to monitor volcanic activity.Editorial responsibility: H. Shinohara     

Fluid geochemistry of Montserrat Island,West Indies

 Two geochemical surveys carried out in March 1991 and September 1992 revealed the existence of a hydrothermal system in the southern portion of Montserrat Island, below Soufrière Hills Volcano. This conclusion is supported by the presence of: (a) the thermal springs of Plymouth which are fed by deep Na–Cl waters (Cl concentration ∼25 000 mg/kg, temperature ca. 250  °C) mixed with shallow steam-heated waters; (b) the four fumarolic fields of Galway's Soufrière, Gages Upper Soufrière, Gages Lower Soufrière, and Tar River Soufrière, where acid to neutral, steam-heated waters are present together with several fumarolic vents, discharging vapors formed through boiling of hydrothermal aqueous solutions. Involvement of magmatic fluids in the recharge of the hydrothermal aquifers is suggested by: (a) the high ³He/⁴He ratios of fumarolic fluids, i.e., 8.2 R_A at Galway's Soufrière and 5.9 R_A at Gages Lower Soufrière; (b) the δD and δ¹⁸O values of Na–Cl thermal springs and steam condensates, indicating the involvement of arc-type magmatic water in the formation of deep geothermal liquids; and (c) the CH₄/CO₂ ratios of fumarolic fluids, which are lower than expected for equilibrium with the FeO–FeO_1.5 hydrothermal rock buffer, but being shifted towards the SO₂–H₂S magmatic gas buffer. Received: 26 March 1996 / Accepted: 19 July 1996     

CO<Subscript>2</Subscript> and He degassing at El Chichón volcano,Chiapas, Mexico: gas flux,origin and relationship with local and regional tectonics

During 2007–2008, three CO₂ flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO₂ flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m⁻² day⁻¹ (April 2008) with total emission rates of 164 ± 9.5 (March 2007), 59 ± 2.5 (December 2007) and 109 ± 6.6 t day⁻¹ (April 2008). The mean CO₂ flux estimated from the entire crater floor area was 1,102 g m⁻² day⁻¹ for April 2008 with a total emission rate of 144 ± 5.9 t day⁻¹. Significant change in CO₂ flux was not detected during the period of survey, and the mapping of the CO₂ flux highlighted lineaments reflecting the main local and regional tectonic patterns. The ³He/⁴He ratio (as high as 8.1 R _A) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO₂/³He ratios for the high ³He/⁴He gases tend to have the MORB-like values (1.41 × 10⁹), and the CO₂/³He ratios for the lower ³He/⁴He gases fall within the range for the arc-type gases. The high ³He/⁴He ratios, the MORB-like CO₂/³He ratios for the high ³He/⁴He gases and high proportion of MORB-CO₂ (M = 25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.     

Diffuse Emission of CO2 from Showa-Shinzan, Hokkaido, Japan: A Sign of Volcanic Dome Degassing

Two soil CO₂ efflux surveys were carried out in September 1999 and June 2002 to study the spatial distribution of diffuse CO₂ degassing and estimate the total CO₂ output from Showa-Shinzan volcanic dome, Japan. Seventy-six and 81 measurements of CO₂ efflux were performed in 1999 and 2002, respectively, covering most of Showa-Shinzan volcano. Soil CO₂ efflux data showed a wide range of values up to 552 g m^-2 d^-1. Carbon isotope signatures of the soil CO₂ ranged from -0.9‰ to -30.9‰, suggesting a mixing between different carbon reservoirs. Most of the study area showed CO₂ efflux background values during the 1999 and 2002 surveys (B = 8.2 and 4.4 g m^-2 d^-1, respectively). The spatial distribution of CO₂ efflux anomalies for both surveys showed a good correlation with the soil temperature, indicating a similar origin for the extensive soil degassing generated by condensation processes and fluids discharged by the fumarolic system of Showa-Shinzan. The total diffuse CO₂ output of Showa-Shinzan was estimated to be about 14.0–15.6 t d^-1 of CO₂ for an area of 0.53 km².     

New geological insights and structural control on fluid circulation in La Fossa cone (Vulcano,Aeolian Islands,Italy)

Electric resistivity tomography (ERT), self-potential (SP), soil CO₂ flux, and temperature are used to study the inner structure of La Fossa cone (Vulcano, Aeolian Islands). Nine profiles were performed across the cone with a measurement spacing of 20 m. The crater rims of La Fossa cone are underlined by sharp horizontal resistivity contrasts. SP, CO₂ flux, and temperature anomalies underline these boundaries which we interpret as structural limits associated to preferential circulation of fluids. The Pietre Cotte crater and Gran Cratere crater enclose the main hydrothermal system, identified at the centre of the edifice on the base of low electrical resistivity values (<20 Ω m) and strong CO₂ degassing, SP, and temperature anomalies. In the periphery, the hydrothermal activity is also visible along structural boundaries such as the Punte Nere, Forgia Vecchia, and Palizzi crater rims and at the base of the cone, on the southern side of the edifice, along a fault attributed to the NW main tectonic trend of the island. Inside the Punte Nere crater, the ERT sections show an electrical resistive body that we interpret as an intrusion or a dome. This magmatic body is reconstructed in 3D using the available ERT profiles. Its shape and position, with respect to the Pietre Cotte crater fault, allows replacing this structure in the chronology of the development of the volcano. It corresponds to a late phase of activity of the Punte Nere edifice. Considering the position of the SP, soil CO₂ flux, and temperature maxima and the repartition of conductive zones related to hydrothermal circulation with respect to the main structural features, La Fossa cone could be considered as a relevant example of the strong influence of pre-existing structures on hydrothermal fluid circulation at the scale of a volcanic edifice.     

Geochemical model of a magmatic–hydrothermal system at the Lastarria volcano, northern Chile

Lastarria volcano (25°10′ S, 68°31′ W; 5,697 m above sea level), located in the Central Andes Volcanic Zone (northern Chile), is characterized by four distinct fumarolic fields with outlet temperatures ranging between 80°C and 408°C as measured between May 2006–March 2008 and April–June 2009. Fumarolic gasses contain significant concentrations of high temperature gas compounds (i.e., SO₂, HCl, HF, H₂, and CO), and isotopic ratios (³He/⁴He, δ¹³C–CO₂, δ¹⁸O–H₂O, and δD–H₂O) diagnostic of magmatic gas sources. Gas equilibria systematics, in both the H₂O-H₂-CO₂-CO-CH₄ and alkane–alkene C₃ system, suggest that Lastarria fumarolic gasses emanate from a superheated vapor that is later cooled and condensed at relatively shallow depths. This two-stage process inhibits the formation of a continuous aquifer (e.g., horizontal liquid layer) at relatively shallow depth. Recent developments in the magmatic gas system may have enhanced the transfer and release of heat causing shallow aquifer vaporization. The consequent pressure increase and aquifer vaporization likely triggered the inflation events beginning in 2003 at the Lastarria volcano.     

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.     

Gas and particle emissions from Soufrière Hills Volcano, Montserrat, West Indies: characterization and health hazard assessment

 The Soufrière Hills Volcano, Montserrat, erupting since 18 July 1995, intensified its degassing in early 1996 with the continuing growth of the lava dome inside the summit crater. During this period of increased activity, between 11 and 18 March 1996, we measured gases and particles within the visible plume to determine whether at that time it posed a health risk to the population of Plymouth, the capital town, which is 5 km southwest (downwind) and was then still occupied. Gravimetric measurements were made of total suspended particles (TSP) and particles having an aerodynamic diameter of less than 10 μm (PM₁₀). Measurements were made of sulphur dioxide (SO₂), hydrochloric acid (HCl), hydrofluoric acid (HF), nitric acid (HNO₃), acetic acid (CH₃COOH), formic acid (HCOOH), and particulate sulphate (SO₄ ^2–), chloride (Cl^–), nitrate (NO₃ ^–), fluoride (F^–), methanesulphonate (CH₃SO₃ ^–), acetate (CH₃COO^–), formate (HCOO^–), ammonium (NH₄ ⁺), sodium (Na⁺) and acidity (H⁺). Trace metals having human health implications [chromium (Cr), nickel (Ni), cobalt (Co), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), cadmium (Cd), tin (Sn), mercury (Hg) and lead (Pb)] were also determined. Mean concentrations of HCl, SO₂ and HF obtained in the town of Plymouth were 14.0, 5.9 and 0.8 ppbv, respectively. Corresponding concentrations in the mixed plume on the crater edge were 533, 168 and 22 ppbv. There were no direct emissions of HNO₃, although nitrate was detected in coarse particles at the source. Higher concentrations of CH₃COOH and HCOOH were measured close to the crater. Mean TSP and PM₁₀ were 64 and 15 μg m^–3 in Plymouth, and 455 and 47 μg m^–3 on the upper volcano slope. Aerosols were highly acidic at the source but rapidly neutralised during transport. Trace metals were enriched in the aerosol relative to crater surface material. The concentrations of the acid gases, sulphur dioxide in particular, and particles were found to be too small to pose a health hazard at the time of these measurements, when relatively modest volcanic activity was occurring. Received: 9 September 1998 / Accepted: 29 August 1999     

Geochemistry of the volcano-hydrothermal system of El Chichón Volcano, Chiapas, Mexico

 The 1982 eruption of El Chichón volcano ejected more than 1 km³ of anhydrite-bearing trachyandesite pyroclastic material to form a new 1-km-wide and 300-m-deep crater and uncovered the upper 500 m of an active volcano-hydrothermal system. Instead of the weak boiling-point temperature fumaroles of the former lava dome, a vigorously boiling crater spring now discharges  / 20 kg/s of Cl-rich (∼15 000 mg/kg) and sulphur-poor ( / 200 mg/kg of SO₄), almost neutral (pH up to 6.7) water with an isotopic composition close to that of subduction-type magmatic water (δD=–15‰, δ¹⁸O=+6.5‰). This spring, as well as numerous Cl-free boiling springs discharging a mixture of meteoric water with fumarolic condensates, feed the crater lake, which, compared with values in 1983, is now much more diluted (∼3000 mg/kg of Cl vs 24 030 mg/kg), less acidic (pH=2.6 vs 0.56) and contains much lower amounts of S ( / 200 mg/kg of SO₄, vs 3550 mg/kg) with δ³⁴S=0.5–4.2‰ (+17‰ in 1983). Agua Caliente thermal waters, on the southeast slope of the volcano, have an outflow rate of approximately 100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data). Relative N₂, Ar and He gas concentrations suggest extensional tectonics for the El Chichón volcanic centre. The ³He/⁴He and ⁴He/²⁰Ne ratios in gases from the crater fumaroles (7.3R_a, 2560) and Agua Caliente hot springs (5.3R_a, 44) indicate a strong magmatic contribution. However, relative concentrations of reactive species are typical of equilibrium in a two-phase boiling aquifer. Sulphur and C isotopic data indicate highly reducing conditions within the system, probably associated with the presence of buried vegetation resulting from the 1982 eruption. All Cl-rich waters at El Chichón have a common source. This water has the appearence of a "partially matured" magmatic fluid: condensed magmatic vapour neutralized by interaction with fresh volcaniclastic deposits and depleted in S due to anhydrite precipitation. Shallow ground waters emerging around the volcano from the thick cover of fresh pumice deposits (Red waters) are Ca–SO₄–rich and have a negative oxygen isotopic shift, probably due to ongoing formation of clay at low temperatures. Received: 21 July 1997 / Accepted: 4 December 1997     

Dynamics of carbon dioxide emissions,crystallization, and magma ascent: hypotheses,theory, and applications to volcano monitoring at Mount St. Helens

 Measurements of CO₂ fluxes from open-vent volcanos are rare, yet may offer special capabilities for monitoring volcanos and forecasting activity. The measured fluxes of CO₂ and SO₂ from Mount St. Helens decreased from July through November 1980, but the record includes variations of CO₂/SO₂ in the emitted gas and episodes of greatly increased fluxes of CO₂. We propose that the CO₂ flux variations reflect two gas components: (a) a component whose flux decreased in proportion to 1/ √t with a CO₂/SO₂ mass ratio of 1.7, and (b) a residual flux of CO₂ consisting of short-lived, large peaks with a CO₂/SO₂ mass ratio of 15. We propose two hypotheses: (a) the 1/ √t dependence was generated by crystallization in a deep magma body at rates governed by diffusion-limited heat transfer, and (b) the gas component with the higher CO₂/SO₂ was released from ascending magma, which replenished the same magma body. The separation of the total CO₂ flux into contributions from known processes permits quantitative inferences about the replenishment and crystallization rates of open-system magma bodies beneath volcanos. The flux separations obtained by using two gas sources with distinct CO₂/SO₂ ratios and a peak minus background approach to obtain the CO₂ contributions from an intermittent source and a continuously emitting source are similar. The flux separation results support the hypothesis that the second component was generated by episodic magma ascent and replenishment of the magma body. The diffusion-limited crystallization hypothesis is supported by the decay of minimum CO₂ and SO₂ fluxes with 1/ √t after 1 July 1980. We infer that the magma body at Mount St. Helens was replenished at an average rate (2.8×10⁶m³d^–1) which varied by less than 5% during July, August, and September 1980. The magma body volume (2.4–3.0 km³) in early 1982 was estimated by integrating a crystallization rate function inferred from CO₂ fluxes to maximum times (20±4 years) estimated from the increase of sample crystallinity with time. These new volcanic gas flux separation methods and the existence of relations among the CO₂ flux, crystallization rates, and magma body replenishment rates yield new information about the dynamics of an open-vent, replenished magma body. Received: 15 February 1995 / Accepted: 30 March 1996     

Contrasting hydrothermal activity at Sierra Negra and Alcedo volcanoes, Galapagos Archipelago, Ecuador

2 and approximately 85% SO₂ of the total sulfur gas. Relative amounts of He, Ar, and N₂ show a distinct hot-spot signature ( ). The δ¹³C–CO₂ is approximately −3.6‰ and δ³⁴S_T is approximately +3.3‰. The δD/δ¹⁸O of fumarole H₂O indicates steam separation from local meteoric waters whose estimated minimum mean residence time from ³H analyses is ≤40 years. Fumarolic activity at Alcedo is controlled by a caldera-margin fault containing at least seven hydrothermal explosion craters, and by an intracaldera rhyolite vent. Two explosion craters which formed in 1993–1994 produce approximately 15 m³/s of steam, yet discharge temperatures are ≤97°C. Water content of the total gas is 95–97 mol.%, noncondensible gas is 92–98 mol.% CO₂, and sulfur gas is dominated by H₂S. Relative amounts of He, Ar, and N₂ show extensive mixing between hot spot and air or air-saturated meteoric water components but the average . The δ¹³C–CO₂ is approximately −3.5‰ and δ³⁴S_T is approximately −0.8‰. The δD/δ¹⁸O of fumarole steam indicates separation from a homogeneous reservoir that is enriched 3–5‰ in ¹⁸O compared with local meteoric water. ³H indicates that this reservoir water has a maximum mean residence time of approximately 400 years and empirical gas geothermometry indicates a reservoir temperature of 260–320°C. The intracaldera hydrothermal reservoir in Alcedo is probably capable of producing up to 150 MW; however, environmental concerns as well as lack of infrastructure and power users will limit the development of this resource. Received: 19 April 1999 / Accepted: 23 October 1999     

Chemical and isotopic variations in fumarolic discharge and thermal waters at Vulcano Island (Aeolian Islands, Italy) during 1996: evidence of resumed volcanic activity

Gas samples from some fumaroles at ‘La Fossa' crater and Baia di Levante on Vulcano Island and from a diffuse soil gas emission were analysed during 1995–1996, along with water samples from thermal wells in the area of Vulcano Porto. During 1996, we observed a significant increase both in the gas/steam ratio and in the CO₂ concentration, as well as strong variations in δ¹³C_CO2, δD_H2O and δ¹⁸O_H2O of fumarolic gases. These variations are probably related to an increased inflow of deep fluids of magmatic origin. The temperatures of fumaroles did not show remarkable variations except for fumarole F11. In this case, temperature increased by about 80°C from February to August 1996. During the same period, remarkable variations in temperature, phreatic level and chemical and isotopic composition of water were also recorded in one of the geothermal wells in the Vulcano Porto area (Camping Sicilia; T60°C). The observed variations in this well are probably related to a pressure build-up, occurring at least in the surficial part of the system, because of increased gas flux and/or decreased permeability of the fumarolic degassing system. Chemical and isotopic composition of the water showed that during this evolutionary phase, the content of fumarolic condensate in this well was about 80 to 90%. Based on the observation of physical and chemical variables of the Camping Sicilia fluids, during this phase of activity, it is concluded that this area is affected by a phreatic eruption hazard if a volcanic episode with high energy discharge in a limited time span occurs. It follows that this well may be considered as a preferential point for volcanic activity monitoring, both in the case of normal routine surveillance and in the case of inaccessibility to the crater area.     

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).     

Eddy covariance imaging of diffuse volcanic CO<Subscript>2</Subscript> emissions at Mammoth Mountain,CA, USA

Use of eddy covariance (EC) techniques to map the spatial distribution of diffuse volcanic CO₂ fluxes and quantify CO₂ emission rate was tested at the Horseshoe Lake tree-kill area on Mammoth Mountain, California, USA. EC measurements of CO₂ flux were made during September–October 2010 and ranged from 85 to 1,766 g m⁻² day⁻¹. Comparative maps of soil CO₂ flux were simulated and CO₂ emission rates estimated from three accumulation chamber (AC) CO₂ flux surveys. Least-squares inversion of measured eddy covariance CO₂ fluxes and corresponding modeled source weight functions recovered 58–77% of the CO₂ emission rates estimated based on simulated AC soil CO₂ fluxes. Spatial distributions of modeled surface CO₂ fluxes based on EC and AC observations showed moderate to good correspondence (R ² = 0.36 to 0.70). Results provide a framework for automated monitoring of volcanic CO₂ emissions over relatively large areas.     

Geochemical monitoring of the 2002–2003 eruption at Stromboli volcano (Italy): precursory changes in the carbon and helium isotopic composition of fumarole gases and thermal waters

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 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.Editorial responsibility: H Shinohara     

CO2 output and δ13C(CO2) from Mount Etna as indicators of degassing of shallow asthenosphere

 An estimated average CO₂ output from Etna's summit craters in the range of 13±3 Mt/a has recently been determined from the measured SO₂ output and measured CO₂/SO₂ molar ratios. To this amount the CO₂ output emitted diffusely from the soil (≈ 1 Mt/a) and the amount of CO₂ dissolved in Etna's aquifers (≈ 0.25 Mt/a) must be added. Data on the solubility of CO₂ in Etnean magmas at high temperature and pressure allow the volume of magma involved in the release of such an amount of this gas to be estimated. This volume of magma (≈ 0.7 km³/a) is approximately 20 times greater than the volume of magma erupted annually during the period 1971–1995. On the basis of C-isotopic data of CO₂ collected in the Etna area and of new hypotheses on the source of Mediterranean magmas, significant contributions of CO₂ from non-magmatic sources to the total output from Etna are unlikely. Such large outputs of CO₂ and also of SO₂ from Etna could be due to an anomalously shallow asthenosphere beneath the volcano that allows a continuous escape of gases toward the surface, even without migration of magma. Received: 7 August 1996 / Accepted: 9 November 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     

Structure and CO<Subscript>2</Subscript> budget of Merapi volcano during inter-eruptive periods

Soil temperature and gas (CO₂ concentration and flux) have been investigated at Merapi volcano (Indonesia) during two inter-eruptive periods (2002 and 2007). Precise imaging of the summit crater and the spatial pattern of diffuse degassing along a gas traverse on the southern slope are interpreted in terms of summit structure and major caldera organization. The summit area is characterized by decreasing CO₂ concentrations with distance from the 1932 crater rim, down to atmospheric levels at the base of the terminal cone. Similar patterns are measured on any transect down the slopes of the cone. The spatial distribution of soil gas anomalies suggests that soil degassing is controlled by structures identified as concentric historical caldera rims (1932, 1872, and 1768), which have undergone severe hydrothermal self-sealing processes that dramatically lower the permeability and porosity of soils. Temperature and CO₂ flux measurements in soils near the dome display heterogeneous distributions which are consistent with a fracture network identified by previous geophysical studies. These data support the idea that the summit is made of isolated and mobile blocks, whose boundaries are either sealed by depositional processes or used as pathways for significant soil degassing. Within this context, self-sealing both prevents long-distance soil degassing and controls heat and volatile transfers near the dome. A rough estimate of the CO₂ output through soils near the dome is 200–230 t day⁻¹, i.e. 50% of the estimated total gas output from the volcano summit during these quiescent periods. On Merapi’s southern slope, a 2,500 m long CO₂ traverse shows low-amplitude anomalies that fit well with a recently observed electromagnetic anomaly, consistent with a faulted structure related to an ancient avalanche caldera rim. Sub-surface soil permeability is the key parameter that controls the transfer of heat and volatiles within the volcano, allowing its major tectonic architecture to be revealed by soil gas and soil temperature surveys.     

Thermal expansion-contraction and slope instability of a fumarole field inferred from geodetic measurements at Vulcano

Between 1987 and 1993, fumarole temperatures at the Fossa crater of Vulcano (Italy) were characterized by the highest values since the 1920’s, increasing from about 300°C in 1987 to 690°C in May 1993, before decreasing to 400°C by 1996–1997. During 1990, Vulcano’s Electronic Distance Measurement (EDM) network was expanded to provide more detailed coverage of the northern sector of the Fossa crater and, in particular, to monitor the movement of the northern flank the Fossa cone. Measurements, carried out between 1990 and 1994, showed shortening by about 6 to 7 cm along baselines measured to a small section of the northern rim. Over the following four years these baselines showed a slow extension by about 3 cm, to gradually recover part of the previous deformation. We believe that the shortening and lengthening of the EDM baselines was respectively due to the increasing and decreasing temperature of the rock body lying close to the deforming area. This caused thermal expansion, followed by contraction. The positive movement of the rim was not completely matched by a negative recovery, suggesting that a non-recoverable sliding movement was also responsible for some of the shortening of the baselines. We verified our hypothesis by calculating the expected dilatation of a rock body, as a function of the volume of rock heated and its thermal expansion coefficient, and compared the expected deformation to that observed. The geodetic investigation showed that the unstable portion affects a small length of the rim (about 100 m long) and involves a volume of about 0.8 × 10⁶ m³. However, this zone lies directly above a particularly unstable portion of the flank, as well as the main village and port on the island.     

Chemical and isotopic compositions of thermal springs,fumaroles and bubbling gases at Tacaná Volcano (Mexico–Guatemala): implications for volcanic surveillance

This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO₃–SO₄ waters are thought to have formed by the absorption of a H₂S/SO₂–CO₂-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO₃-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ¹⁸O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at ~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ¹⁸O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO₂-dominated. The δ¹³C_CO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in ³He/⁴He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric ³He/⁴He ratio (R _A)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (⁴He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO₂/³He ratio of gases: bubbling springs with lower gas/water ratios show higher ³He/⁴He ratios and consequently lower CO₂/³He ratios (e.g. Zarco spring). Typical Central American CO₂/³He and ³He/⁴He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 10¹⁰ and 6.0 ± 0.9 R _A, respectively). The L/S (5.9 ± 0.5) and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc, Tacaná.