Geochemistry of the thermal springs and fumaroles of Basse-Terre Island,Guadeloupe, Lesser Antilles

 The purpose of this work was to study jointly the volcanic-hydrothermal system of the high-risk volcano La Soufrière, in the southern part of Basse-Terre, and the geothermal area of Bouillante, on its western coast, to derive an all-embracing and coherent conceptual geochemical model that provides the necessary basis for adequate volcanic surveillance and further geothermal exploration. The active andesitic dome of La Soufrière has erupted eight times since 1660, most recently in 1976–1977. All these historic eruptions have been phreatic. High-salinity, Na–Cl geothermal liquids circulate in the Bouillante geothermal reservoir, at temperatures close to 250  °C. These Na–Cl solutions rise toward the surface, undergo boiling and mixing with groundwater and/or seawater, and feed most Na–Cl thermal springs in the central Bouillante area. The Na–Cl thermal springs are surrounded by Na–HCO₃ thermal springs and by the Na–Cl thermal spring of Anse à la Barque (a groundwater slightly mixed with seawater), which are all heated through conductive transfer. The two main fumarolic fields of La Soufrière area discharge vapors formed through boiling of hydrothermal aqueous solutions at temperatures of 190–215  °C below the "Ty" fault area and close to 260  °C below the dome summit. The boiling liquid producing the vapors of the Ty fault area has δD and δ¹⁸O values relatively similar to those of the Na–Cl liquids of the Bouillante geothermal reservoir, whereas the liquid originating the vapors of the summit fumaroles is strongly enriched in ¹⁸O, due to input of magmatic fluids from below. This process is also responsible for the paucity of CH₄ in the fumaroles. The thermal features around La Soufrière dome include: (a) Ca–SO₄ springs, produced through absorption of hydrothermal vapors in shallow groundwaters; (b) conductively heated, Ca–Na–HCO₃ springs; and (c) two Ca–Na–Cl springs produced through mixing of shallow Ca–SO₄ waters and deep Na–Cl hydrothermal liquids. The geographical distribution of the different thermal features of La Soufrière area indicates the presence of: (a) a central zone dominated by the ascent of steam, which either discharges at the surface in the fumarolic fields or is absorbed in shallow groundwaters; and (b) an outer zone, where the shallow groundwaters are heated through conduction or addition of Na–Cl liquids coming from hydrothermal aquifer(s). Received: 9 November 1998 / Accepted: 15 July 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     

Fumarolic activity of Avachinsky and Koryaksky volcanoes, Kamchatka, from 1993 to 1994

 Volcanic gas and condensate samples were collected in 1993–1994 from fumaroles of Koryaksky and Avachinsky, basaltic andesite volcanoes on the Kamchatka Peninsula near Petropavlovsk–Kamchatsky. The highest-temperature fumarolic discharges, 220  °C at Koryaksky and 473  °C at Avachinsky, are water-rich (940–985 mmol/mol of H₂O) and have chemical and isotopic characteristics typical of Kamchatka–Kurile, high- and medium-temperature volcanic gases. The temperature and chemical and water isotopic compositions of the Koryaksky gases have not changed during the past 11 years. They represent an approximate 2 : 1 mixture of magmatic and meteoric end members. Low-temperature, near-boiling-point discharges of Avachinsky Volcano are water poor (≈880 mmol/mol); Their compositions have not changed since the 1991 eruption, and are suggested to be derived from partially condensed magmatic gases at shallow depth. Based on a simple model involving mixing and single-step steam separation, low water and high CO₂ contents, as well as the observed Cl concentration and water isotopic composition in low-temperature discharges, are the result of near-surface boiling of a brine composed of the almost pure condensed magmatic gas. High methane content in low-temperature Avachinsky gases and the 220  °C Koryaksky fumarole, low C isotopic ratio in CO₂ at Koryaksky (–11.8‰), and water isotope data suggest that the "meteoric" end member contains considerable amounts of the regional methane-rich thermal water discovered in the vicinity of both volcanoes. Received: 2 May 1996 / Accepted: 5 November 1996     

Geochemistry of gases and waters discharged by the mud volcanoes at Paternò, Mt. Etna (Italy)

 Approximately 20 km south of Mt. Etna craters, at the contact between volcanic and sedimentary formations, three mud volcanoes discharge CO₂-rich gases and Na–Cl brines. The compositions of gas and liquid phases indicate that they are fed by a hydrothermal system for which temperatures of 100–150  °C were estimated by means of both gas and solute geothermometry. The hydrothermal system may be associated with CO₂-rich groundwaters over a large area extending from the central part of Etna to the mud volcanoes. Numerous data on the He, CH₄, CO₂ composition of the gases of the three manifestations, sampled over the past 5 years, indicate clearly that variations are due to separation processes of a CO₂-rich gas phase from the liquid. The effects of these processes have to be taken into account in the interpretation of the monitoring data collected for the geochemical surveillance of Etna volcano. Received: 4 September 1995 / Accepted: 14 February 1996     

Geochemical and isotopic evidence for seawater contamination of the hydrothermal system of Taal Volcano, Luzon, the Philippines

 The hydrologic structure of Taal Volcano has favored development of an extensive hydrothermal system whose prominent feature is the acidic Main Crater Lake (pH<3) lying in the center of an active vent complex, which is surrounded by a slightly alkaline caldera lake (Lake Taal). This peculiar situation makes Taal prone to frequent, and sometimes catastrophic, hydrovolcanic eruptions. Fumaroles, hot springs, and lake waters were sampled in 1991, 1992, and 1995 in order to develop a geochemical model for the hydrothermal system. The low-temperature fumarole compositions indicate strong interaction of magmatic vapors with the hydrothermal system under relatively oxidizing conditions. The thermal waters consist of highly, moderately, and weakly mineralized solutions, but none of them corresponds to either water–rock equilibrium or rock dissolution. The concentrated discharges have high Na contents (>3500 mg/kg) and low SO₄/Cl ratios (<0.3). The Br/Cl ratio of most samples suggests incorporation of seawater into the hydrothermal system. Water and dissolved sulfate isotopic compositions reveal that the Main Crater Lake and spring discharges are derived from a deep parent fluid (T≈300  °C), which is a mixture of seawater, volcanic water, and Lake Taal water. The volcanic end member is probably produced in the magmatic-hydrothermal environment during absorption of high-temperature gases into groundwater. Boiling and mixing of the parent water give rise to the range of chemical and isotopic characteristics observed in the thermal discharges. Incursion of seawater from the coastal region to the central part of the volcano is supported by the low water levels of the lakes and by the fact that Lake Taal was directly connected to the China sea until the sixteenth century. The depth to the seawater-meteoric water interface is calculated to be 80 and 160 m for the Main Crater Lake and Lake Taal, respectively. Additional data are required to infer the hydrologic structure of Taal. Geochemical surveillance of the Main Crater Lake using the SO₄/Cl, Na/K, or Mg/Cl ratio cannot be applied straightforwardly due to the presence of seawater in the hydrothermal system. Received: 12 February 1997 / Accepted: 26 January 1998     

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.     

Evolution of fluid geochemistry at the Turrialba volcano (Costa Rica) from 1998 to 2008

Turrialba (10°02′N, 83°45′W) is a 3,349-m high stratovolcano belonging to the Holocene “Cordillera Central” volcanic belt of Costa Rica. The summit consists of three EW-oriented craters (East, Central, and West). Since its last eruptive phase (1864–1866), the Central and West craters have displayed modest fumarolic activity, with outlet temperatures clustering around 90°C. In 2001, seismic swarms, ground deformation, and increasing fumarolic activity occurred. From 2005 to 2008, new fumarolic vents opened between and within the Central and West craters, and along the western and southwestern outer flanks of the volcanic edifice. These physical changes were accompanied by a drastic modification in the gas chemistry that can be divided in three stages: (1) hydrothermal (from 1998 to autumn 2001), characterized by the presence of H₂O, CO₂, H₂S, and, to a very minor extent, HCl and HF; (2) hydrothermal/magmatic (autumn 2001–2007), with the appearance of SO₂ and a significant increase of HCl and HF; and (3) magmatic-dominated (2007–2008), characterized by increased SO₂ content, SO₂/H₂S > 100, and temperatures up to 282°C. Accordingly, gas equilibrium in the CO₂-CH₄-H₂ system suggests a progressive evolution of the deep fluid reservoir toward higher temperatures and more oxidizing conditions. The chemical–physical modifications of Turrialba in the last decade can be interpreted as part of a cyclic mechanism controlling the balance between the hydrothermal and the magmatic systems. Nevertheless, the risk of rejuvenation of the volcanic activity cannot be excluded, and an appropriate seismic, ground deformation, and geochemical monitoring program is highly recommended. Turrialba lies at a distance of 35 and 15 km from San José and Cartago, respectively, the two largest cities in Costa Rica.     

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     

Petrology and sulfur and chlorine emissions of the 1963 eruption of Gunung Agung,Bali, Indonesia

 The 1963 eruption of Gunung Agung produced 0.95 km³ dense rock equivalent (DRE) of olivine±hornblende-bearing, weakly phyric, basaltic andesite tephra and lava. Evidence for magma mixing in the eruptive products includes whole-rock compatible and incompatible trace element trends, reverse and complex compositional zoning of mineral phases, disequilibrium mineral assemblages, sieve-textured plagioclase phenocrysts, and augite rims on reversely zoned orthopyroxene. Basalt magma mixed with pre-existing andesite magma shortly before eruption to yield basaltic andesite with a temperature of 1040–1100  °C at an assumed pressure of 2 kb, f O₂>NNO, and an average melt volatile content (H₂O±CO₂) of 4.3 wt.%. Magma-mixing end members may have provided some of the S and Cl emitted in the eruption. Glass inclusions in phenocrysts contain an average of 650 ppm S and 3130 ppm Cl as compared with 70 ppm and 2220 ppm, respectively, in the matrix glass. Maximum S and Cl contents of glass inclusions approach 1800 and 5000 ppm, respectively. Application of the petrologic method to products of the 1963 eruption for estimating volatile release yields of 2.5×10¹²g (Mt) of SO₂ and 3.4 Mt of Cl released from the 0.65 km³ of juvenile tephra which contributed to stratospheric injection of H₂SO₄ aerosols on 17 March and 16 May, when eruption column heights exceeded 20 km above sea level. An independent estimate of SO₂ release from atmospheric aerosol loading (11–12 Mt) suggests that approximately 7 Mt of SO₂ was injected into the stratosphere. The difference between the two estimates can be most readily accounted for by the partitioning of S, as well as some Cl, from the magma into a water-rich vapor phase which was released upon eruption. For other recent high-S-release eruptions of more evolved and oxidized magmas (El Chichón, Pinatubo), the petrologic method gives values two orders of magnitude less than independent estimates of SO₂ emissions. Results from this study of the Agung 1963 magma and its volatile emissions, and from related studies on eruptions of more mafic magmas, suggest that SO₂ emissions from eruptions of higher-S-solubility magma may be more reliably estimated by the petrologic method than may those from more-evolved magma eruptions. Received: 29 June 1994 / Accepted: 25 April 1996     

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.     

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.     

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     

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.     

Physical properties of the 1980 Mount St. Helens cryptodome magma

 Physical properties of cryptodome and remelted samples of the Mount St. Helens grey dacite have been measured in the laboratory. The viscosity of cryptodome dacite measured by parallel–plate viscometry ranges from 10.82 to 9.94 log₁₀ η (Pa s) (T=900–982  °C), and shrinkage effects were dilatometrically observed at T>900  °C. The viscosity of remelted dacite samples measured by the micropenetration method is 10.60–9.25 log₁₀ η (Pa s) (T=736–802  °C) and viscosities measured by rotational viscometry are 3.22–1.66 log₁₀ η (Pa s) (T=1298–1594  °C). Comparison of the measured viscosity of cryptodome dacitic samples with the calculated viscosity of corresponding water-bearing melt demonstrates significant deviations between measured and calculated values. This difference reflects a combination of the effect of crystals and vesicles on the viscosity of dacite as well as the insufficient experimental basis for the calculation of crystal-bearing vesicular melt viscosities at low temperature. Assuming that the cryptodome magma of the 18 May 1980 Mount St. Helens eruption was residing at 900  °C with a phenocryst content of 30 vol.%, a vesicularity of 36 vol.% and a bulk water content of 0.6 wt.%, we estimate the magma viscosity to be 10^10.8 Pa s. Received: 25 August 1996 / Accepted: 19 July 1997     

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     

Characteristics,extent and origin of hydrothermal alteration at Mount Rainier Volcano,Cascades Arc,USA: Implications for debris-flow hazards and mineral deposits

Hydrothermal alteration at Mount Rainier waxed and waned over the 500,000-year episodic growth of the edifice. Hydrothermal minerals and their stable-isotope compositions in samples collected from outcrop and as clasts from Holocene debris-flow deposits identify three distinct hypogene argillic/advanced argillic hydrothermal environments: magmatic-hydrothermal, steam-heated, and magmatic steam (fumarolic), with minor superimposed supergene alteration. The 3.8 km³ Osceola Mudflow (5600 y BP) and coeval phreatomagmatic F tephra contain the highest temperature and most deeply formed hydrothermal minerals. Relatively deeply formed magmatic-hydrothermal alteration minerals and associations in clasts include quartz (residual silica), quartz–alunite, quartz–topaz, quartz–pyrophyllite, quartz–dickite/kaolinite, and quartz–illite (all with pyrite). Clasts of smectite–pyrite and steam-heated opal–alunite–kaolinite are also common in the Osceola Mudflow. In contrast, the Paradise lahar, formed by collapse of the summit or near-summit of the edifice at about the same time, contains only smectite–pyrite and near-surface steam-heated and fumarolic alteration minerals. Younger debris-flow deposits on the west side of the volcano (Round Pass and distal Electron Mudflows) contain only low-temperature smectite–pyrite assemblages, whereas the proximal Electron Mudflow and a < 100 y BP rock avalanche on Tahoma Glacier also contain magmatic-hydrothermal alteration minerals that are exposed in the avalanche headwall of Sunset Amphitheater, reflecting progressive incision into deeper near-conduit alteration products that formed at higher temperatures.     

N<Subscript>2</Subscript>, Ar,and He as a tool for discriminating sources of volcanic fluids with application to Vulcano,Italy

A detailed analysis of published data on the N₂, Ar, and He content and Ar and He isotopic composition of fumarolic fluids from Vulcano crater (south Italy) supports a model with two endmembers comprising magmatic and hydrothermal fluids with correspondingly low and high H₂O content. The magmatic component with the highest ³He/⁴He and highest absolute concentrations of N₂, Ar, and He also has the lowest N₂/Ar and N₂/He ratios (∼300 and ∼500, respectively). In contrast, the hydrothermal endmember, with the lower ³He/⁴He and lower absolute N₂, Ar, and He abundances, has high N₂/Ar (∼1,000) and high N₂/He (>3,000) ratios. The hydrothermal component is also characterized by the highest ⁴⁰Ar/³⁶Ar ratios (>1,000) and is proposed to be the main carrier of metamorphic gases from the arc crust.     

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     

Volatile emission during the eruption of Baitoushan Volcano (China/North Korea) ca. 969 AD

3 [magma volume (DRE): 24 ± 5 km³]. The main phase (ca. 95 vol.%) is represented by comenditic tephra deposited dominantly as widespread fallout blankets and proximal ignimbrites. The eruption column is estimated to have reached ca. 25 km and thus entered the stratosphere. A late phase (5 vol.%) is represented by trachyte emplaced chiefly as moderately welded ignimbrites. The comendites contain  ∼ 3, and the trachytes 10–20 vol.% phenocrysts, mainly anorthoclase, hedenbergite, and fayalite. Primary glassy melt inclusions with no signs of leakage were found only in phenocrysts in the comenditic tephra, whereas those in phenocrysts in the trachytes are devitrified. The comendite magma is interpreted to have been generated by fractional crystallization from a trachyte magma represented by melt inclusions in the phenocrysts in the comendite tephra. The mass of volatiles emitted to the atmosphere during the eruption was estimated using the petrologic method. The average H₂O concentration of the comenditic matrix glass is 1.5 wt.% (probably largely secondary) and of the corresponding melt inclusions  ∼ 5.2 wt.%. Melt inclusions in feldspar and quartz present the highest halogen concentrations with a calculated average for chlorine of 4762 ppm and for fluorine of 4294 ppm. The comenditic matrix glasses are represented by a fluorine-rich (3992 ppm F) and fluorine-poor group (2431 ppm F), averaging 3853 ppm for chlorine. Only 20% of all sulfur analyses of the comenditic matrix glasses and melt inclusions are above the detection limit of  ≥ 250 ppm S. The difference between pre- and post-eruptive concentration of H₂O is at least 3.7 ± 0.6 wt.% H₂O taking into consideration re-hydration of the matrix glass and possible leakage of melt inclusions. The difference between pre- and post-eruptive concentrations of the halogens amounts to 909 ± 90 ppm Cl, and 1863 ± 280 ppm and 302 ± 40 ppm F. The difference for S was estimated based on the average of the maximum S concentrations in the melt inclusions (455 ppm S) and the detection limit, resulting in 205 ± 40 ppm S. The calculated mass of volatiles injected into the atmosphere, based on the erupted magma volume and volatile data, is 1796 ± 453 megatons for H₂O, 45 ± 10 megatons for chlorine, 42 ± 11 megatons for fluorine, and 2 ± 0.6 megatons for sulfur. The 969 ± 20 AD eruption of Baitoushan Volcano, one of the largest eruptions of the past 2000 years, is thought to have had a substantial but possibly short-lived effect on climate. Received: 25 July 1998 / Accepted: 8 September 1999     

Viscosity of microlite-bearing rhyolitic obsidians: an experimental study

 To investigate the influence of microlites on lava flow rheology, the viscosity of natural microlite-bearing rhyolitic obsidians of calc-alkaline and peralkaline compositions containing 0.1–0.4 wt.% water was measured at volcanologically relevant temperatures (650–950  °C), stresses (10³–10⁵ Pa) and strain rates (10^–5 to 10^–7 s^–1). The glass transition temperatures (T _g ) were determined from scanning calorimetric measurements on the melts for a range of cooling/heating rates. Based on the equivalence of enthalpic (calorimetric) and shear (viscosity) relaxation, we calculated the viscosity of the melt in crystal-bearing samples from the T _g data. The difference between the calculated viscosity of the melt phase and the measured viscosity for the crystal-bearing samples is interpreted to be the physical effect of microlites on the measured viscosity. The effect of <5 vol.% rod-like microlites on the melt rheology is negligible. Microlite-rich and microlite-poor samples from the same lava flow and with identical bulk chemistry show a difference of 0.6 log₁₀ units viscosity (Pa s), interpreted to be due to differences in melt chemistry caused by the presence of microlites. The only major differences between measured and calculated viscosities were for two samples: a calc-alkaline rhyolite with 1 vol.% branching crystals, and a peralkaline rhyolite containing crystal-rich bands with >45 vol.% crystals. For both of these samples a connectivity factor is apparent, with, for the latter, a close packing framework of crystals which is interpreted to influence the apparent viscosity. Received: 14 March 1996 / Accepted: 30 May 1996