Hydrochemical dynamics of the “lake–spring” system in the crater of El Chichón volcano (Chiapas,Mexico)

El Chichón volcano (Chiapas, Mexico) erupted violently in March–April 1982, breaching through the former volcano–hydrothermal system. Since then, the 1982 crater has hosted a shallow (1–3.3 m, acidic (pH ∼ 2.2) and warm (∼ 30 °C) crater lake with a strongly varying chemistry (Cl/SO₄ = 0–79 molar ratio). The changes in crater lake chemistry and volume are not systematically related to the seasonal variation of rainfall, but rather to the activity of near-neutral geyser-like springs in the crater (Soap Pool). These Soap Pool springs are the only sources of Cl for the lake. Their geyser-like behaviour with a long-term (months to years) periodicity is due to a specific geometry of the shallow boiling aquifer beneath the lake, which is the remnant of the 1983 Cl-rich (24,000 mg/l) crater lake water. The Soap Pool springs decreased in Cl content over time. The zero-time extrapolation (1982, year of the eruption) approaches the Cl content in the initial crater lake, meanwhile the extrapolation towards the future indicates a zero-Cl content by 2009 ± 1. This particular situation offers the opportunity to calculate mass balance and Cl budget to quantify the lake–spring system in the El Chichón crater. These calculations show that the water balance without the input of SP springs is negative, implying that the lake should disappear during the dry season. The isotopic composition of lake waters (δD and δ¹⁸O) coincide with this crater lake-SP dynamics, reflecting evaporation processes and mixing with SP geyser and meteoric water. Future dome growth, not observed yet in the post-1982 El Chichón crater, may be anticipated by changes in lake chemistry and dynamics.     

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.     

Anomalous Emissions of SO2 During the Recent Eruption of Santa Ana Volcano, El Salvador, Central America

Santa Ana volcano in western El Salvador, Central America, had a phreatic eruption at 8:05 am (local time) on October 1, 2005, 101 years after its last eruption. However, during the last one hundred years this volcano has presented periods of quiet degassing with fumarolic activity and an acidic lake within its crater. This paper presents results of frequent measurements of SO₂ degassing using the MiniDOAS (Differential Optical Absorption Spectroscopy) system and a comparison with the volcanic seismicity prior to the eruption, during, and after the eruption. Vehicle measurements of SO₂ flux were taken every hour during the first nine days of the eruption and daily after that. The period of time reported here is from August to December, 2005. Three periods of degassing are distinguished: pre-eruptive, eruptive, and post-eruptive periods. The intense activity at Santa Ana volcano started in July 2005. During the pre-eruptive period up to 4306 and 5154 ton/day of SO₂ flux were recorded on October 24 and September 9, 2005, respectively. These values were of the same order of magnitude as the recorded values just after the October 1^st eruption (2925 ton/day at 10:01 am). Hourly measurements of SO₂ flux taken during the first nine days after the main eruptive event indicate that explosions are preceded by an increase in SO₂ flux and that this parameter reaches a peak after the explosion took place. This behavior suggests that increasing accumulation of exsolved magmatic gases occurs within the magmatic chamber before the explosions, increasing the pressure until the point of explosion. A correlation between SO₂ fluxes and RSAM (Real Time Seismic Amplitude Measurements) is observed during the complete sampling period. Periodic fluctuations in the SO₂ and RSAM values during the entire study period are observed. One possible mechanism explaining these fluctuations it that convective circulation within the magmatic chamber can bring fresh magma periodically to shallow levels, allowing increasing degasification and then decreasing degasification as the batch of magma lowers its gas content, becomes denser, and sinks to give space to a new magma pulse. These results illustrate that the measurements of SO₂ flux can provide important warning signals for incoming explosive activity in active volcanoes.     

Geochemistry of fluids associated with the 1995–1996 eruption of Mt. Ruapehu, New Zealand: signatures and processes in the magmatic-hydrothermal system

The 1995–1996 eruption of Mt. Ruapehu has provided a number of insights into the geochemical processes operating within the magmatic-hydrothermal system of this volcano. Both pre-eruption degassing of the rising magma and its eventual intrusion into the convective zone of the hydrothermal system beneath the lake were clearly reflected in lake water compositions. The eruptions of September–October 1995 expelled the lake, and provided the first-ever opportunity to characterise gas discharges from this volcano. The fumarolic discharges revealed compositions typical of andesite volcanoes and strong interaction with the enclosing meteoric and hydrothermal system fluids. Some 1.1 MT of SO₂ gas was released from the volcano between September 1995 and December 1996, whereas ca. twice this amount (2.2 MT equivalent SO₂) was erupted as soluble (i.e. leachable) oxyanions of sulphur. Significantly more sulphur was released from the volcano over this period than can be accounted for from the magma volume actually erupted. The evidence suggests that a sizable component of the evolved sulphur was remobilised from the long-lived hydrothermal system within the volcano during the 1995–1996 activity.     

Estimating thermal inflow to El Chichón crater lake using the energy-budget,chemical and isotope balance approaches

El Chichón crater lake appeared immediately after the 1982 catastrophic eruption in a newly formed, 1-km wide, explosive crater. During the first 2 years after the eruption the lake transformed from hot and ultra-acidic caused by dissolution of magmatic gases, to a warm and less acidic lake due to a rapid “magmatic-to-hydrothermal transition” — input of hydrothermal fluids and oxidation of H₂S to sulfate. Chemical composition of the lake water and other thermal fluids discharging in the crater, stable isotope composition (δD and δ¹⁸O) of lake water, gas condensates and thermal waters collected in 1995–2006 were used for the mass-balance calculations (Cl, SO₄ and isotopic composition) of the thermal flux from the crater floor. The calculated fluxes of thermal fluid by different mass-balance approaches become of the same order of magnitude as those derived from the energy-budget model if values of 1.9 and 2 mmol/mol are taken for the catchment coefficient and the average H₂S concentration in the hydrothermal vapors, respectively. The total heat power from the crater is estimated to be between 35 and 60 MW and the CO₂ flux is not higher than 150 t/day or ~ 200 gm^− 2 day^− 1.     

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     

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.     

Hydroacoustic noise precursors of the 1990 eruption of Kelut Volcano, Indonesia

The results of a hydroacoustic monitoring experiment in the Kelut Crater lake, Indonesia, prior to its 1990 eruption, are presented, with the benefit of hindsight. Indeed, the underwater noise levels in three widely separated frequency bands, together with the lake water temperature, was radio-transmitted and almost continuously recorded from a period of quiescence of the volcano till the onset of its 10 February 1990, eruption, which destroyed the monitoring buoy. The comparative analysis of the noise variations in the three bands, together with seismic and temperature data, have shed light on the mechanisms underlying the pre-eruptive activity. The three acoustic levels had shown conspicuous, yet distinctive, changes prior to the eruption. Acoustic level in the low-frequency (1–50 Hz) band, which increased one year before the resumption of seismic activity and the lake warming up, is interpreted as the result of boiling at depth. The source of high-acoustic level in the audiometric (500–5000 Hz) range is clearly the bubbling of volcanic gases, occurring as a strong convective column in the middle of the lake. From the variations of this audiometric level, we have estimated that the degassing rate in the lake increased by a hundred-fold during the pre-eruptive period. Variations of ultrasonic (20–100 kHz) frequency acoustic level seem to be related with pressure and thermal changes within the hydrothermal system and its rock matrix beneath the lake. In conclusion, this experiment demonstrates the potential of hydroacoustic monitoring as an early warning system at crater lake volcanoes.     

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.     

Subaqueous geothermal activity revealed by lacustrine sediments of the acidic Nakadake crater lake, Aso Volcano, Japan

Lacustrine sediments were sampled from the inaccessible acidic (pH = 0.43) Nakadake crater lake of Aso Volcano, Japan by a simple method. The sediments contain an extremely high content (74 wt.%) of sulfur, which exits as elemental sulfur, gypsum and anhydrite. The abundant elemental sulfur is likely formed by the reaction of SO₂ and H₂S gases and by the SO₂ disproportionation reaction in magmatic hydrothermal system below the crater lake. Based on the sulfur content of sediments and measurements of elevation change of the crater bottom, the sulfur accumulation rate at the Nakadake crater lake was calculated as 250 tonne/day, which is comparable with the SO₂ emission rate (200–600 tonne/day) from the Nakadake crater. The sediments include a small amount (9%) of clear glass shards that are apparently not altered in spite of the high reactivity of hyperacid lake water. This finding suggests that the clear glass shards are fragments of recently emitted magmas from fumaroles on the bottom of the crater lake and the magma emissions continuously occur even in quiescent periods.     

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     

Downstream composition changes of acidic volcanic waters discharged into the Banyupahit stream, Ijen caldera, Indonesia

The crater lake of Kawah Ijen volcano contains extremely low pH (<0.4) waters with high SO₄ (70000 mg/kg), Cl (21000 mg/kg), F (1500 mg/kg), Al (5000 mg/kg), Fe (2000 mg/kg) and trace metal (Cu 0.5, Zn 4, Pb 3 mg/kg) contents. These brines seep outward through the western crater rim and reappear on the other side as streamlets, which form the headwaters of the Banyupahit stream. The Banyupahit first mixes with fresh rivers and thermal springs in the Ijen caldera and then irrigates a coastal agricultural plain which is 30 km from the summit crater.We discuss the downstream composition changes affecting the Banyupahit waters by using stable isotope, chemical and mineralogical data collected from sites along the stream length. The saturation of the stream waters with respect to minerals was evaluated with SOLVEQ and WATEQ4F and compared with the geochemical observations. An aluminous mineralogy (alunogen, pickeringite, tamarugite and kalinite) develops in the upper part of the Banyupahit due to concentration of the headwaters by evaporation. Downstream attenuation of dissolved element concentrations results principally from dilution and from mineral precipitation. The stream pH changes from 0 at the source to >4 close to the mouth. The δD and δ¹⁸O values and the relative SO₄–Cl–F contents of the Banyupahit waters indicate that the tributaries are mostly meteoric. Dissolved SO₄ in the acidic stream come only from the crater lake seepages and are not involved later in microbially mediated reactions, as shown by their δ³⁴S and δ¹⁸O values. Re-equilibration of the stream SO₄ oxygen-isotope composition with H₂O from tributaries does not occur.Calcium, SiO₂, Al, Fe, K and SO₄ behave non-conservatively in the stream waters. Gypsum, silica (amorphous or poorly ordered), a basic aluminum hydroxysulfate (basaluminite?), K-jarosite and amorphous ferric hydroxide may exert a solubility control on these elements along the entire stream length, or in certain stream sections, consistent with the thermochemical model results. Downstream concentration trends and mineral saturation levels suggest that precipitation of Sr-, Pb-rich barite and celestite consume Ba, Sr and Pb, whereas dissolved Cu, Pb and Zn may adsorb onto solid particles, especially after the junctions of the acidic stream with non-acidic rivers. We calculated that significant fluxes of SO₄, F, Cl, Al, SiO₂, Ti, Mn and Cu may reach the irrigation system, possibly causing serious environmental impacts such as soil acidification and induration.     

Addition of magmatic volatiles into the hot spring waters of loowit canyon,Mount St. Helens,Washington, USA

Geochemical studies on cold meteoric waters, post-1980 hot spring waters, fumarole emissions from the dacite dome, and volcanic rocks at Mount St. Helens (MSH) from 1985 to 1989 show that magmatic volatiles are involved in the formation of a new hydrothermal system. Hot spring waters are enriched in ¹⁸O by as much as 2 and display enrichments in D relative to cold waters. A well-defined isotopic trend is displayed by the isotopic composition of a>400°C fumarole condensate collected from the central crater in 1980 (-33 D, +6 ¹⁸O), of condensate samples collected on the dome, and of cold meteoric and hot spring waters. The trend indicates that mixing occurs between local meteoric water and magmatic water degassing from the dacite dome. Between 30 and 70% magmatic water is present in the dome fumarole discharges and 10% magnatic water has been added to the waters of the hydrothermal system. Relations between Cl, SO₄ and HCO₃ indicate that the hot spring waters are immature volcanic waters formed by reaction of rocks with waters generated by absorption of acidic volcanic fluids. In addition, the B/Cl ratios of the spring waters are similar to the B/Cl ratios of the fumarole condensates (0.02), values of ¹³C in the HCO₃ of the hot springs (-9.5 to-13.5) are similar to the magmatic value at MSH (-10.5), and the ³He/⁴He ratio, relative to air, in a hot spring water is 5.7, suggesting a magmatic origin for this component.managed by Martin Marietta Energy Systems, Inc., under contract DE-AC05-84OR21400 with the US Department of Energy     

The chemical and hydrologic structure of Poa´s Volcano, Costa Rica

Comparison of the chemical characteristics of spring and river water draining the flanks of Poa´s Volcano, Costa Rica indicates that acid chloride sulfate springs of the northwestern flank of the volcano are derived by leakage and mixing of acid brines formed in the summit hydrothermal system with dilute flank groundwater. Acid chloride sulfate waters of the Rio Agrio drainage basin on the northwestern flank are the only waters on Poa´s that are affected by leakage of acid brines from the summit hydrothermal system. Acid sulfate waters found on the northwestern flank are produced by the interaction of surface and shallow groundwater with dry and wet acid deposition of SO₂ and H₂SO₄ aerosols, respectively. The acid deposition is caused by a plume of acid gases that is released by a shallow magma body located beneath the active crater of Poa´s.No evidence for a deep reservoir of neutral pH sodium chloride brine is found at Poa´s. The lack of discharge of sodium chloride waters at Poa´s is attributed to two factors: (1) the presence of a relatively volatile-rich magma body degassing at shallow depths (< 1 km) into a high level summit groundwater system; and (2) the hydrologic structure of the volcano in which high rates of recharge combine with rapid lateral flow of shallow groundwater to prevent deep-seated sodium chloride fluids from ascending to the surface. The shallow depth of the volatile-rich magma results in the degassing of large quantities of SO₂ and HCl. These gases are readily hydrolyzed and quickly mix with meteoric water to form a reservoir of acid chloride-sulfate brine in the summit hydrothermal system. High recharge rates and steep hydraulic gradients associated with elevated topographic features of the summit region promote lateral flow of acid brines generated in the summit hydrothermal system. However, the same high recharge rates and steep hydraulic gradients prevent lateral flow of deep-seated fluids, thereby masking the presence of any sodium chloride brines that may exist in deeper parts of the volcanic edifice.Structural, stratigraphic, and topographic features of Poa´s Volcano are critical in restricting flow of acid brines to the northwestern flank of the volcano. A permeable lava-lahar sequence that outcrops in the Rio Agrio drainage basin forms a hydraulic conduit between the crater lake and acid chloride sulfate springs. Spring water residence times are estimated from tritium data and indicate that flow of acid brines from the active crater to the Rio Agrio source springs is relatively rapid (3 to 17 years). Hydraulic conductivity values of the lava-lahar sequence calculated from residence time estimates range from 10⁻⁵ to 10⁻⁷ m/s. These values are consistent with hydraulic conductivity values determined by aquifer tests of fractured and porous lava/pyroclastic sequences at the base of the northwestern flank of the volcano.Fluxes of dissolved rock-forming elements in Rio Agrio indicate that approximately 4300 and 1650 m³ of rock are removed annually from the northwest flank aquifer and the active crater hydrothermal system, respectively. Over the lifetime of the hydrothermal system (100's to 1000's of years), significant increases in aquifer porosity and permeability should occur, in marked contrast to the reduction in permeability that often accompanies hydrothermal alteration in less acidic systems. Average fluxes of fluoride, chloride and sulfur calculated from discharge and compositional data collected in the Rio Agrio drainage basin over the period 1988–1990 are approximately 2, 38 and 30 metric tons/day. These fluxes should be representative of minimum volatile release rates at Poa´s in the last 10 to 20 years.     

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.     

Remarkable geochemical changes and degassing at Voui crater lake,Ambae volcano,Vanuatu

Ambae (also known as Aoba), is a 38 × 16 km² lozenge-shaped island volcano with a coastal population of around 10 000. At the summit of the volcano is lake Voui — one of the largest active crater lakes worldwide, with 40 × 10⁶ m³ of acidic water perched 1400 m a.s.l. After more than 300 years of dormancy, Ambae volcano reawakened with phreatic eruptions through Voui in 1995, and culminating in a series of surtseyan eruptions in 2005, followed by a rapid and spectacular colour change of the lake from light blue to red in 2006. Integrating lake water chemistry with new measurements of SO₂ emissions from the volcano during the 2005–2006 eruptive period helps to explain the unusual and spectacular volcanic activity of Ambae — initially, a degassed magma approached the lake bed and triggered the surtseyan eruption. Depressurization of the conduit facilitated ascent of volatile-rich magma from the deeper plumbing system. The construction of a cone during eruption and the high degassing destabilised the equilibrium of lake stratification leading to a limnic event and subsequently the spectacular colour change.     

Textural and geochemical constraints on eruptive style of the 79 <Emphasis Type="SmallCaps">ad</Emphasis> eruption at Vesuvius

The 79 ad Plinian eruption of Vesuvius produced first a white pumice fallout from a high steady eruptive column, and then a grey pumice fallout originating from an oscillatory eruptive column with several partial column collapse events after which there was a total column collapse. This first total collapse was followed by renewed Plinian activity and produced the last grey pumice (GP) fallout deposit of the eruption. Textural characteristics (vesicularity and microcrystallinity) of a complete sequence of the pumice fallout deposits are presented along with the major element compositions and residual volatile contents (H₂O, Cl) to constrain the degassing processes and the eruptive dynamics. Large variations in residual volatile contents exist between the different eruptive units. Textural features also strongly differ between white and grey pumices, but also within the grey pumices. The degassing processes were thus highly heterogeneous. We propose a new model of the 79 ad eruption in which pre-eruptive conditions (H₂O saturation, magma temperature and viscosity) are the critical controls on the diversity of the syn-eruptive degassing processes and hence the eruptive dynamics. Cl contents measured in melt inclusions show that only the white pumice and the upper part of the grey pumice magma were H₂O saturated prior to eruption. The white pumice eruptive units represent a typical closed-system degassing evolution, whereas the first grey pumice one, stored under similar pre-eruptive saturation conditions, follows a particular open-system degassing evolution. We suggest that the oscillatory regime that dominated the grey pumice eruptive phase is linked to pre-eruptive water undersaturation of most of the grey magma, and the associated time delays necessary for H₂O exsolution. We also suggest that the high residual H₂O content of the last grey pumice, deposited after the renewal of Plinian activity following the first total column collapse event, is due to syn-eruptive saturation of GP magma and reduced H₂O exsolution efficiency resulting from speciation of dissolved H₂O in the melt.     

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.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Gas emissions from failed and actual eruptions from Cook Inlet Volcanoes,Alaska, 1989–2006

Cook Inlet volcanoes that experienced an eruption between 1989 and 2006 had mean gas emission rates that were roughly an order of magnitude higher than at volcanoes where unrest stalled. For the six events studied, mean emission rates for eruptions were ∼13,000 t/d CO₂ and 5200 t/d SO₂, but only ∼1200 t/d CO₂ and 500 t/d SO₂ for non-eruptive events (‘failed eruptions’). Statistical analysis suggests degassing thresholds for eruption on the order of 1500 and 1000 t/d for CO₂ and SO₂, respectively. Emission rates greater than 4000 and 2000 t/d for CO₂ and SO₂, respectively, almost exclusively resulted during eruptive events (the only exception being two measurements at Fourpeaked). While this analysis could suggest that unerupted magmas have lower pre-eruptive volatile contents, we favor the explanations that either the amount of magma feeding actual eruptions is larger than that driving failed eruptions, or that magmas from failed eruptions experience less decompression such that the majority of H₂O remains dissolved and thus insufficient permeability is produced to release the trapped volatile phase (or both). In the majority of unrest and eruption sequences, increases in CO₂ emission relative to SO₂ emission were observed early in the sequence. With time, all events converged to a common molar value of C/S between 0.5 and 2. These geochemical trends argue for roughly similar decompression histories until shallow levels are reached beneath the edifice (i.e., from 20–35 to ∼4–6 km) and perhaps roughly similar initial volatile contents in all cases. Early elevated CO₂ levels that we find at these high-latitude, andesitic arc volcanoes have also been observed at mid-latitude, relatively snow-free, basaltic volcanoes such as Stromboli and Etna. Typically such patterns are attributed to injection and decompression of deep (CO₂-rich) magma into a shallower chamber and open system degassing prior to eruption. Here we argue that the C/S trends probably represent tapping of vapor-saturated regions with high C/S, and then gradual degassing of remaining dissolved volatiles as the magma progresses toward the surface. At these volcanoes, however, C/S is often accentuated due to early preferential scrubbing of sulfur gases. The range of equilibrium degassing is consistent with the bulk degassing of a magma with initial CO₂ and S of 0.6 and 0.2 wt.%, respectively, similar to what has been suggested for primitive Redoubt magmas.