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100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data).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     

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     

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     

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     

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.     

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     

Temporal geochemical variations in volatile emissions from Mount St. Helens, USA, 1980–1994

Fumarole discharges (95–560°C) collected from the dacite dome inside Mount St. Helens crater show temporal changes in their isotopic and chemical compositions. A δD vs. δ¹⁸O plot shows that condensed waters from the gases are mixtures of meteoric and magmatic components, but that the apparent magmatic end-member in 1994 was depleted by about 7‰ in δD relative to the apparent end-member in 1980. Based on δD modeling, approximately 63% of shallow, post-1980 magma has yet to degas. Surprisingly, Cl and F contents in the 1994 samples were only 0.47 and 3.8%, respectively, of the concentrations determined for end-member magmatic fluid in 1980. The data indicate that Cl (and F and B) is degassed from magma relatively quickly compared to water and/or that most of the Cl degassed in later years is dissolved into the shallow Mount St. Helens hydrothermal system. Because metals are often transported in magmatic and hydrothermal fluids as Cl complexes, rapid changes in surface volatile compositions may have implications for the timing and location of metals transport and deposition in some volcanoes.     

Modelling the dynamics and thermodynamics of volcanic degassing

 The rates of passive degassing from volcanoes are investigated by modelling the convective overturn of dense degassed and less dense gas-rich magmas in a vertical conduit linking a shallow degassing zone with a deep magma chamber. Laboratory experiments are used to constrain our theoretical model of the overturn rate and to elaborate on the model of this process presented by Kazahaya et al. (1994). We also introduce the effects of a CO₂–saturated deep chamber and adiabatic cooling of ascending magma. We find that overturn occurs by concentric flow of the magmas along the conduit, although the details of the flow depend on the magmas' viscosity ratio. Where convective overturn limits the supply of gas-rich magma, then the gas emission rate is proportional to the flow rate of the overturning magmas (proportional to the density difference driving convection, the conduit radius to the fourth power, and inversely proportional to the degassed magma viscosity) and the mass fraction of water that is degassed. Efficient degassing enhances the density difference but increases the magma viscosity, and this dampens convection. Two degassing volcanoes were modelled. At Stromboli, assuming a 2 km deep, 30% crystalline basaltic chamber, containing 0.5 wt.% dissolved water, the ∼700 kg s^–1 magmatic water flux can be modelled with a 4–10 m radius conduit, degassing 20–100% of the available water and all of the 1 to 4 vol.% CO₂ chamber gas. At Mount St. Helens in June 1980, assuming a 7 km deep, 39% crystalline dacitic chamber, containing 4.6 wt.% dissolved water, the ∼500 kg s^–1 magmatic water flux can be modelled with a 22–60 m radius conduit, degassing ∼2–90% of the available water and all of the 0.1 to 3 vol.% CO₂ chamber gas. The range of these results is consistent with previous models and observations. Convection driven by degassing provides a plausible mechanism for transferring volatiles from deep magma chambers to the atmosphere, and it can explain the gas fluxes measured at many persistently active volcanoes. Received: 26 September 1997 / Accepted: 11 July 1998     

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     

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 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.     

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     

The influence of trace amounts of water on the viscosity of rhyolites

 As a major volatile in volcanic systems, water has a significant influence on the rheological properties of silicic magmas. This is especially so at minor water contents relevant to the emplacement of silicic lavas. To investigate the influence of water on the viscosity of natural rhyolitic obsidians, a novel strategy has been adopted employing parallel-plate and micropenetration techniques. Viscosities have been determined on three types of material: (a) raw water-bearing obsidians; (b) remelted (1650  °C, 1 atm) degassed glasses of the obsidians; and (c) hydrothermally hydrated (1300  °C, 3 kbar) obsidians. Ten natural rhyolitic obsidians (peraluminous, calc-alkaline and peralkaline) were employed: seven originated from lava flows and contained <0.2 wt.% H₂O, two samples were F-rich from pyroclastic successions, and one was an obsidian cobble with 1.5 wt.% water also associated with pyroclastic units. Melt compositions and water contents were stable during viscometry. The measured decreases in activation energies of viscous flow and viscosity with small amounts of water are much greater than the Shaw calculation scheme predicts. In addition, a marked non-linear decrease in η exists with increasing water content. In contrast to the case for peralkaline rhyolites, 0.1–0.2 wt.% water decreases activation energies significantly (up to 30%) for calc-alkaline compositions. These results have important implications for the ease of near-surface degassing of silicic magmas during emplacement and permit the testing of calculational models for viscosity, largely based on synthetic systems. Received: 7 July 1997 / Accepted: 6 April 1998     

Holocene tephrochronology record of large explosive eruptions in the southernmost Patagonian Andes

For regionally widespread Holocene tephra layers in southernmost Patagonia, correlations based on both chemical and chronological data indicate their derivation from five large-volume (>1 km³) explosive eruptions of four different volcanoes in the southernmost Andes. Bulk-tephra and tephra-glass major and trace-element chemistry and Sr isotopic ratios unambiguously distinguish different source volcanoes, and imply that two of the regionally widespread tephra (MB₁ and MB₂) were derived from Mt. Burney (52°S), one (R₁) from Reclus (51°S), one (A₁) from Aguilera (50°S) and one (H₁) from Hudson volcano (46°S). The H₁ tephra derived from the Hudson volcano, which is located at the southern end of the Andean Southern Volcanic Zone (SVZ; 33–46°S), contains distinctive greenish andesitic glass with FeO > 4.5 wt.% and TiO₂ > 1.2 wt.%. In contrast, rhyolitic glass in tephra derived from the eruptions of Mt. Burney, Reclus and Aguilera volcanoes, which are located in the Andean Austral Volcanic Zone (AVZ; 49–55°S), is clear and transparent and has significantly lower FeO and TiO₂. Tephra derived from these three AVZ volcanoes all contain plagioclase, orthopyroxene, minor clinopyroxene and amphibole. Biotite occurs only in the Aguilera A₁ tephra, which also has the highest bulk-tephra and tephra-glass K₂O and Rb contents. Averages of new and published ¹⁴C ages determined on organic material in soil and sediment samples above and below these tephra constrain the uncalibrated ¹⁴C age of the R₁ eruption of Reclus volcano to 12,685 ± 260 years BP, the MB₁ and MB₂ eruptions of Mt. Burney to 8,425 ± 500 and 3,830 ± 390 years BP, the Hudson H₁ eruption to 6,850 ± 160 years BP, and the A₁ eruption of Aguilera volcano to 3,000 ± 100 years BP. The volume of the largest of these eruptions, H₁ of the Hudson volcano, is estimated as >18 km³. The volume of the Reclus R₁ eruption is estimated at >10 km³, the Aguilera A₁ eruption at between 4 and 9 km³, and the younger Mt. Burney MB₂ eruption at ≥2.8 km³. The volume of the older MB₁ Mt. Burney eruption is the least well constrained, but must have been larger than the younger MB₂ eruption. The data indicate that the frequency of explosive activity of volcanic centers in the AVZ is lower than in the southern SVZ.     

Mantle-derived magmatic gas releasing features at the Rehai area, Tengchong county, Yunnan Province, China

This paper deals with the chemical and isotopic compositions of escaped gases from the Rehai geothermal area in Tengchong county of Yunnan Province. Results indicate that there is the mantle-derived magmatic intrusion in shallow crust at this area. Modern mantle-derived magmatic volatiles are being released currently in a steady stream by way of active faults. The escaped gases are mostly composed of CO₂, together with subordinate amounts of H₂S, N₂, H₂, CH₄, SO₂, CO and He. At the studied area, the north-south directed fault is the deepest, and it may be interlinked with the deep-seated thermal reservoir that would be directly recharged by the mantle-derived magmatic volatile. The He, C isotopic evidence reveals that the modern active magma beneath Rehai area may originate from the historical mantle-derived magma which caused the latest eruptive activity of volcanoes in that region.     

A model of diffuse degassing at three subduction-related volcanoes

2 and δ¹³C in soil gas were measured at three active subduction-related stratovolcanoes (Arenal and Poás, Costa Rica; Galeras, Colombia). In general, Rn, CO₂ and δ¹³C values are higher on the lower flanks of the volcanoes, except near fumaroles in the active craters. The upper flanks of these volcanoes have low Rn concentrations and light δ¹³C values. These observations suggest that diffuse degassing of magmatic gas on the upper flanks of these volcanoes is negligible and that more magmatic degassing occurs on the lower flanks where major faults and greater fracturing in the older lavas can channel magmatic gases to the surface. These results are in contrast to findings for Mount Etna where a broad halo of magmatic CO₂ has been postulated to exist over much of the edifice. Differences in radon levels among the three volcanoes studied here may result from differences in age, the degree of fracturing and faulting, regional structures or the level of hydrothermal activity. Volcanoes, such as those studied here, act as plugs in the continental crust, focusing magmatic degassing towards crater fumaroles, faults and the fractured lower flanks. Received: 16 December 1997 / Accepted: 27 January 2000     

First <Superscript>13</Superscript>C/<Superscript>12</Superscript>C isotopic characterisation of volcanic plume CO<Subscript>2</Subscript>

We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO₂ in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ¹³C of volcanic CO₂ between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported in previous work highlights a temporal trend of systematic increase of δ¹³C values of Etna CO₂ from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ¹³C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the carbon isotopic composition of the CO₂ emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity.     

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H₂ and S gas contents in ash eruption clouds and lower H₂ and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H₂O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.     

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     

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.