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.     

The magmatic- and hydrothermal-dominated fumarolic system at the Active Crater of Lascar volcano,northern Chile

Low-to-high temperature fumaroles discharging from the Active Crater of Lascar volcano (northern Chile) have been collected in November 2002, May 2005 and October 2006 for chemical and isotopic analysis to provide the first geochemical survey on the magmatic-hydrothermal system of this active volcano. Chemical and isotopic gas composition shows direct addition of high-temperature fluids from magmatic degassing, mainly testified by the very high contents of SO₂, HCl and HF (up to 87,800, 29,500 and 2,900 μmol/mol) and the high R/Ra values (up to 7.29). Contributions from a hydrothermal source, mainly in gas discharges of the Active Crater rim, has also been detected. Significant variations in fluid chemistry, mainly consisting of a general decrease of magmatic-related compounds, i.e. SO₂, have affected the fumarolic system during the period of observation, indicating an increase of the influence of the hydrothermal system surrounding the ascending deep fluids. The chemical composition of Active Crater fumaroles has been used to build up a geochemical model describing the main processes that regulate the fluid circulation system of Lascar volcano to be utilized in volcanic surveillance.     

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

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

Vanadium sublimates from the fumaroles of Izalco volcano, El Salvador

Prior to the recent discovery of high-temperature vanadium sublimates at the fumaroles of Izalco volcano, El Salvador, the only vanadium minerals known were those formed at low-temperature surface conditions. Six new vanadium compounds have already been discovered at Izalco volcano, and five of these have been elevated to mineral status. Two of the minerals are among the most vanadium-rich compounds known in nature.Field studies and studies of the crystal chemistry of the sublimate phases have allowed delineation of the conditions of exsolution of vanadium-bearing gases from the magma and conditions of sublimation of the vanadium compounds. A vanadium halogen or oxyhalogen gas phase was exsolved from a basaltic magma when the magma was 550 m below the summit crater. As the gas rose to the fumaroles and mixed with the atmosphere, the oxygen fugacity rose from that of the magma to at least 10^−3,5 bar. At the fumaroles, the vanadium compounds sublimated at various temperatures, but a minimum temperature of 760° can be determined for one of the phases based on geothermometry determined from phase relations in the system CuO-V₂O₅. The studies have demonstrated that a vanadium-bearing gas can segregate from a magma with normal basaltic concentrations of vanadium.     

Evaluation of gases,condensates, and SO2 emissions from Augustine volcano,Alaska: the degassing of a Cl-rich volcanic system

After the March–April 1986 explosive eruption a comprehensive gas study at Augustine was undertaken in the summers of 1986 and 1987. Airborne COSPEC measurements indicate that passive SO₂ emission rates declined exponentially during this period from 380±45 metric tons/day (T/D) on 7/24/86 to 27±6 T/D on 8/24/87. These data are consistent with the hypothesis that the Augustine magma reservoir has become more degassed as volcanic activity decreased after the spring 1986 eruption. Gas samples collected in 1987 from an 870°C fumarole on the andesitic lava dome show various degrees of disequilibrium due to oxidation of reduced gas species and condensation (and loss) of H₂O in the intake tube of the sampling apparatus. Thermochemical restoration of the data permits removal of these effects to infer an equilibrium composition of the gases. Although not conclusive, this restoration is consistent with the idea that the gases were in equilibrium at 870°C with an oxygen fugacity near the Ni–NiO buffer. These restored gas compositions show that, relative to other convergent plate volcanoes, the Augustine gases are very HCl rich (5.3–6.0 mol% HCl), S rich (7.1 mol% total S), and H₂O poor (83.9–84.8 mol% H₂O). Values of D and ¹⁸O suggest that the H₂O in the dome gases is a mixture of primary magmatic water (PMW) and local seawater. Part of the Cl in the Augustine volcanic gases probably comes from this shallow seawater source. Additional Cl may come from subducted oceanic crust because data by Johnston (1978) show that Cl-rich glass inclusions in olivine crystals contain hornblende, which is evidence for a deep source (>25km) for part of the Cl. Gas samples collected in 1986 from 390°–642°C fumaroles on a ramp surrounding the inner summit crater have been oxidized so severely that restoration to an equilibrium composition is not possible. H and O isotope data suggest that these gases are variable mixtures of seawater, FMW, and meteoric steam. These samples are much more H₂O-rich (92%–97% H₂O) than the dome gases, possibly due to a larger meteoric steam component. The 1986 samples also have higher Cl/S, S/C, and F/Cl ratios, which imply that the magmatic component in these gases is from the more degassed 1976 magma. Thus, the 1987 samples from the lava dome are better indicators than the 1986 samples of degassing within the Augustine magma reservoir, even though they were collected a year later and contain a significant seawater component. Future gas studies at Augustine should emphasize fumaroles on active lava domes. Condensates collected from the same lava-dome fumarole have enrichments ot 10⁷–10² in Cl, Br, F, B, Cd, As, S, Bi, Pb, Sb, Mo, Zn, Cu, K, Li, Na, Si, and Ni. Lower-temperature (200°–650°C) fumaroles around the volcano are generally less enriched in highly volatile elements. However, these lower-termperature fumaroles have higher concentration of rock-forming elements, probably derived from the wall rock.     

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

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

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

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

Fumarolic gases at Mombacho volcano (Nicaragua): presence of magmatic gas species and implications for volcanic surveillance

Mombacho is a deeply dissected volcano belonging to the Quaternary volcanic chain of Nicaragua. The southern, historic collapse crater (El Crater) currently hosts a fumarolic field with a maximum temperature of 121°C. Chemical and isotopic data from five gas-sampling field campaigns carried out in 2002, 2003 and 2005 highlight the presence of high-temperature gas components (e.g. SO₂, HCl and HF), which indicate a significant contribution of juvenile magmatic fluids to the hydrothermal system feeding the gas discharges. This is strongly supported by the mantle-derived helium and carbon isotopic signatures, although the latter is partly masked by either a sedimentary subduction-related or a shallow carbonate component. The observed chemical and isotopic composition of the Mombacho fluids seems to indicate that this volcanic system, although it has not experienced eruptive events during the last centuries, can be considered active and possibly dangerous, in agreement with the geophysical data recorded in the region. Systematic geochemical monitoring of the fumarolic gas discharges, coupled with a seismic and ground deformation network, is highly recommended in order to monitor a possible new eruptive phase.     

Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Since the March–April 1982 eruption of El Chichòn volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na⁺, Cl⁻, Ca²⁺ and SO₄²⁻ contents, experienced a dramatic change in 1998–1999, turning from a Na⁺–Cl⁻- to a Ca²⁺–SO₄²⁻-rich composition. In June 2000, a relatively sharp increase in Na⁺ and Cl⁻ contents was observed. At the same time, SO₂/H₂S ratios and H₂ and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichòn is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichòn: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichòn after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.     

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.     

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.     

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     

Eruptive history and magmatic evolution of the 1.9 kyr Plinian dacitic Chiltepe Tephra from Apoyeque volcano in west-central Nicaragua

The youngest dacitic Plinian eruption in west-central Nicaragua, forming the 18 km³ Chiltepe Tephra (CT), occurred about nineteen hundred years ago at Apoyeque stratovolcano, which dominates the Chiltepe volcanic complex 15 km north of the capital Managua, where the CT is 2 m thick. We have traced the CT from its proximal facies at the crater rim, through the medial facies in the lowlands around Apoyeque, and to the distal facies up to 550 km offshore in the Pacific. While medial and distal facies consist of widespread Plinian fall deposits, the proximal facies reveals the complexity of this eruption, which we divide into four phases (I–IV). Interaction of rising magma with a pre-existing crater lake generated the phreatomagmatic opening phase I of the eruption, which produced ash fall with accretionary lapilli. Phase II marked a rapid change to persistent magmatic activity that yielded several large Plinian eruptions, declining through a period of unstable eruption conditions, followed by a short hiatus. Phase III began with unstable conditions, probably as a result of eastward migration and widening of the vent, leading to a second period of Plinian eruptions with three major events reaching magma discharge rates five times larger than those of phase II. Phase III again declined through unstable eruption conditions before magmatic activity terminated. Numerous explosions in the shallow hydrothermal system during the final phase IV resulted in the formation of a phreatic tuff ring on the rim of Apoyeque crater. The white, highly-vesicular, dacitic CT pumice contains plagioclase (An_45–68), orthopyroxene, clinopyroxene, and minor hornblende, apatite and titanomagnetite phenocrysts. A very subordinate fraction of gray pumice has the highest crystal content, the least evolved bulk-rock, but the most evolved matrix-glass composition. The CT dacite has two unusual compositional features: (1) all white dacite has the same melt (matrix-glass) composition such that variations in bulk-rock compositions (64–68 wt% SiO₂) simply reflect different phenocryst contents of 10–35%, interpreted as the result of gradual phenocryst settling in the magma chamber. (2) Abundant olivine crystals with a bimodal distribution in Mg# (modes at Mg# = 0.75 and Mg# = 0.8) are dispersed throughout the erupted dacite. These are clearly out of equilibrium with the dacitic melt and are interpreted as xenocrysts derived from the basaltic Nejapa-Miraflores volcanic lineament that intersects the Chiltepe volcanic complex and was contemporaneously active. Thermobarometric estimates place the dacitic CT magma reservoir in the upper crust (<250 MPa), with a temperature of about 890°C and about 5 wt% water dissolved in the melt. Comparing water and chlorine contents with respective solubility models suggests that volatile degassing began in the magma reservoir and triggered the CT eruption. From the vertical compositional variation pattern of the CT we deduce that the conduit tapped the magma chamber not at the top but from the side, at some deeper level, and that subsequent magma withdrawal was governed by both variations in discharge rate and possible upward migration and/or widening of the conduit entrance.     

Chemistry and mineralogy of high-temperature gas discharges from Colima volcano, Mexico. Implications for magmatic gas–atmosphere interaction

Gases, condensates and silica tube precipitates were collected from 400°C (Z2) and 800°C (Z3) fumaroles at Colima volcano, Mexico, in 1996–1998. Volcanic gases at Colima were very oxidized and contain up to 98% air due to mixing with air inside the dome interior, close to the hot magmatic body. An alkaline trap method was used to collect gas samples, therefore only acidic species were analysed. Colima volcanic gases are water-rich (95–98 mol%) and have typical S/C/Cl/F ratios for a subduction type volcano. δD-values for the high-temperature Z3 fumarolic vapour vary from −26 to −57‰. A negative δD–Cl correlation for the Z3 high-temperature fumarole may result from magma degassing: enrichment in D and decrease in the Cl concentration in condensates are likely a consequence of input of “fresh” batches of magma and an increasing of volcanic activity, respectively.The trace element composition of Colima condensates generally does not differ from that of other volcanoes (e.g. Merapi, Kudryavy) except for some enrichment in V, Cu and Zn. Variations in chemical composition of precipitates along the silica tube from the high-temperature fumarole (Colima 1, fumarole Z3), in contrast to other volcanoes, are characterized by high concentrations of Ca and V, low concentration of Mo and a lack of Cd. Mineralogy of precipitates differs significantly from that described for silica tube experiments at other volcanoes with reduced volcanic gas. Thermochemical modelling was used to explain why very oxidized gas at Colima does not precipitate halite, sylvite, and Mo- and Cd-minerals, but does precipitate V-minerals and native gold, which have not been observed before in mineral precipitates from reduced volcanic gases.     

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

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

Geochemical surveillance of active volcanoes: data on the fumaroles of Vulcano (Aeolian Islands,Italy)

Temperature and chemical composition of condensates of higher temperature fumaroles, located on the rim of the crater of Vulcano, were studied over a period of one year. Maximum temperature changed from 216°C (June 1977) to 291°C (May 1978). HCl is the main constituent of condensates which, in comparison with data from fumaroles of other volcanoes, contain also noteworthy quantities of boron and bromine. Since these chemical characteristics suggested the possible inflow of water of marine origin into the volcanic conduit, experimental data on seawater-rock reactions at high temperatures and pressures were taken into account. A model is drafted for the volcanic system, in which the occurrence of an aquifer interposed between the magma chamber and the surface is considered. The vaporization of this aquifer would feed the fumaroles giving rise, through different mixing processes with surface waters, to the observed differences in temperature and chemical composition. However, data available at present are not sufficient to support the proposed model, which must be mainly considered as a working hypothesis.     

The crater lake and hydrothermal system of Mount Pinatubo,Philippines: evolution in the decade after eruption

The June 1991 eruption of Mount Pinatubo, Philippines breached a significant, pre-eruptive magmatic-hydrothermal system consisting of a hot (>300 °C) core at two-phase conditions and surrounding, cooler (<260 °C) liquid outflows to the N and S. The eruption created a large, closed crater that accumulated hydrothermal upwellings, near-surface aquifer and meteoric inflows. A shallow lake formed by early September 1991, and showed a long-term increase in level of ~1 m/month until an artificial drainage was created in September 2001. Comparison of the temporal trends in lake chemistry to pre- and post-eruptive springs distinguishes processes important in lake evolution. The lake was initially near-neutral pH and dominated by meteoric influx and Cl–SO₄ and Cl–HCO₃ hydrothermal waters, with peaks in SO₄ and Ca concentrations resulting from leaching of anhydrite and aerosol-laden tephra. Magmatic discharge, acidity (pH~2) and rock dissolution peaked in late 1992, during and immediately after eruption of a lava dome on the crater floor. Since cessation of dome growth, trends in lake pH (increase from 3 to 5.5), temperature (decline from 40 to 26 °C), and chemical and isotopic composition indicate that magmatic degassing and rock dissolution have declined significantly relative to the input of meteoric water and immature hydrothermal brine. Higher concentrations of Cl, Na, K, Li and B, and lower concentrations of Mg, Ca, Fe, SO₄ and F up to 1999 highlight the importance of a dilute hydrothermal contribution, as do stable-isotope and tritium compositions of the various fluids. However, samples taken since that time indicate further dilution and steeper trends of increasing pH and declining temperature. Present gas and brine compositions from crater fumaroles and hot springs indicate boiling of an immature Cl–SO₄ geothermal fluid of near-neutral pH at approximately 200 °C, rather than direct discharge from magma. It appears that remnants of the pre-eruptive hydrothermal system invaded the magma conduit shortly after the end of dome emplacement, blocking the direct degassing path. This, along with the large catchment area (~5 km²) and the high precipitation rate of the area, led to a rapid transition from a small and hot acid lake to a large lake with near-ambient temperature and pH. This behavior contrasts with that of peak-activity lakes that have more sustained volcanic gas influx (e.g., Kawah Ijen, Indonesia; Poas and Rincón de la Vieja, Costa Rica).Editorial responsibility: H. Shinohara     

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     

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

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

The 1984 to 1996 cyclic activity of Lascar Volcano, northern Chile: cycles of dome growth, dome subsidence, degassing and explosive eruptions

 Lascar Volcano (5592 m; 23°22'S, 67°44'W) entered a new period of vigorous activity in 1984, culminating in a major explosive eruption in April 1993. Activity since 1984 has been characterised by cyclic behaviour with recognition of four cycles up to the end of 1993. In each cycle a lava dome is extruded in the active crater, accompanied by vigorous degassing through high-temperature, high-velocity fumaroles distributed on and around the dome. The fumaroles are the source of a sustained steam plume above the volcano. The dome then subsides back into the conduit. During the subsidence phase the velocity and gas output of the fumaroles decrease, and the cycle is completed by violent explosive activity. Subsidence of both the dome and the crater floor is accommodated by movement on concentric, cylindrical or inward-dipping conical fractures. The observations are consistent with a model in which gas loss from the dome is progressively inhibited during a cycle and gas pressure increases within and below the lava dome, triggering a large explosive eruption. Factors that can lead to a decrease in gas loss include a decrease in magma permeability by foam collapse, reduction in permeability due to precipitation of hydrothermal minerals in the pores and fractures within the dome and in country rock surrounding the conduit, and closure of open fractures during subsidence of the dome and crater floor. Dome subsidence may be a consequence of reduction in magma porosity (foam collapse) as degassing occurs and pressurisation develops as the permeability of the dome and conduit system decreases. Superimposed upon this activity are small explosive events of shallow origin. These we interpret as subsidence events on the concentric fractures leading to short-term pressure increases just below the crater floor. Received: 12 December 1996 / Accepted: 6 May 1997