Bathymetric and geochemical investigation of Kawah Ijen Crater Lake, East Java, Indonesia

A bathymetric survey of Kawah Ijen crater lake was conducted by acoustic sounding in 1996 to compare the lake morphology with those measured in 1922, 1925 and 1938, and to calculate the present lake volume. Even though the lake experienced several hydrothermal eruptions, the maximum depth became shallower (182 m) than before (200 m), resulting in a reduced lake volume (3.0×10⁷ m³).Fifty-two major and minor constituents including rare earth elements and polythionates (PT) of the lake waters at various depths were determined by ICP-AES, ICP-MS and HPLC, respectively. These ions except for several volatile elements are taken up by lake fringe through congruent dissolution of pyroclastics of Kawah Ijen volcano. Most ions are homogeneously distributed throughout the lake, although PT showed a considerable vertical variation. Rare earth elements (REE) in the Kawah Ijen water as well as those from other hyper-acidic crater lakes show distribution patterns likely due to the three rock dissolution (preferential, congruent and residual) types, and their logarithmic concentrations linearly depend upon the pH values of the lake waters.Using the PT degradation kinetics data, production rates of PT, injection rates of SO₂ and H₂S into the lake were estimated to be 114, 86 and 30 tons/day, respectively. Also travel time of the spring water at the Banyupahit Riverhead from Kawah Ijen was estimated to be 600–1000 days through the consideration of decreasing rates of PT. Molten sulfur stocks containing Sn, Cu, Bi sulfides and Pb-barite exposed on the inner crater slope were presumed to be extinct molten sulfur pools at the former lake bottom. This was strongly supported by the barite precipitation temperature estimated through the consideration of the temperature dependence of Pb-chlorocomplex formation.     

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.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

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     

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     

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.     

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.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

Thermal waters hosted by Menderes metamorphic rocks emerge along fault lineaments in the Simav geothermal area. Thermal springs and drilled wells are located in the Eynal, Çitgöl and Na a locations, which are part of the Simav geothermal field. Studies were carried out to obtain the main chemical and physical characteristics of thermal waters. These waters are used for heating of residences and greenhouses and for balneological purposes. Bottom temperatures of the drilled wells reach 163°C with total dissolved solids around 2225 mg/kg. Surface temperatures of thermal springs vary between 51°C and 90°C. All the thermal waters belong to Na–HCO₃–SO₄ facies. The cold groundwaters are Ca–Mg–HCO₃ type. Dissolution of host rock and ion-exchange reactions in the reservoir of the geothermal system shift the Ca–Mg–HCO₃ type cold groundwaters to the Na–HCO₃–SO₄ type thermal waters. Thermal waters are oversaturated at discharge temperatures for aragonite, calcite, quartz, chalcedony, magnesite and dolomite minerals giving rise to a carbonate-rich scale. Gypsum and anhydrite minerals are undersaturated with all of the thermal waters. Boiling during ascent of the thermal fluids produces steam and liquid waters resulting in an increase of the concentrations of the constituents in discharge waters. Steam fraction, y, of the thermal waters of which temperatures are above 100°C is between 0.075 and 0.119. Reservoir pH is much lower than pH measured in the liquid phase separated at atmospheric conditions, since the latter experienced heavy loss of acid gases, mainly CO₂. Assessment of the various empirical chemical geothermometers and geochemical modelling suggest that reservoir temperatures vary between 175°C and 200°C.     

Water quality and hydrogeochemical characteristics of the River Buyukmelen,Duzce, Turkey

The River Buyukmelen is located in the province of Duzce in northwest Turkey and its water basin is approximately 470 km². The Aksu, Kucukmelen and Ugursuyu streams flow into the River Buyukmelen. It flows into the Black Sea with an output of 44 m³ s⁻¹. The geological succession in the basin comprises limestone and dolomitic limestone of the Yılanlı formation, sandstone, clayey limestone and marls of the Akveren formation, clastics and volcano‐clastics of the Caycuma formation, and cover units comprised of river alluvium, lacutrine sediments and beach sands. The River Buyukmelen is expected to be a water source that can supply the drinking water needs of Istanbul until 2040; therefore, it is imperative that its water quality be preserved. The samples of rock, soil, stream water, suspended, bed and stream sediments and beach sand were collected from the Buyukmelen river basin. They were examined using mineralogical and geochemical methods. The chemical constituents most commonly found in the stream waters are Na⁺, Mg²⁺, SO²⁻₄, Cl⁻ and HCO₃⁻ in the Guz stream water, Ca²⁺ in the Abaza stream water, and K⁺ in the Kuplu stream water. The concentrations of Na⁺, K⁺, Ca²⁺, Mg²⁺, SO²⁻₄, HCO⁻₃, Cl⁻, As, Pb, Ni, Mn, Cr, Zn, Fe and U in the Kuplu and Guz stream waters were much higher than the world average values. The Dilaver, Gubi, Tepekoy, Maden, Celik and Abaza streams interact with sedimentary rocks, and the Kuplu and Guz streams interact with volcanic rocks. The amount of suspended sediment in the River Buyukmelen in December 2002 was 120 mg l⁻¹. The suspended and bed sediments in the muddy stream waters are formed of quartz, calcite, plagioclase, clay (kaolinite, illite and smectite), muscovite and amphibole minerals. As, Co, Cd, Cr, Pb, Ni, Zn and U have all accumulated in the Buyukmelen river‐bed sediments. The muddy feature of the waters is related to the petrographic features of the rocks in the basin and their mineralogical compositions, as most of the sandstones and volcanic rocks (basalt, tuffite and agglomerate) are decomposed to a clay‐rich composition at the surface. Thus, the suspended sediment in stream waters increases by physical weathering of the rocks and water–rock interaction. Owing to the growing population and industrialization, water demand is increasing. The plan is to bring water from the River Buyukmelen to Istanbul's drinking‐water reservoirs. According to the Water Pollution Regulations, the River Buyukmelen belongs to quality class 1 based on Hg, Cd, Pb, As, Cu, Cr, Zn, Mn, Se, Ba, Na⁺, Cl⁻, and SO²⁻₄; and to quality class 3 based on Fe concentration. The concentration of Fe in the River Buyukmelen exceeds the limit values permitted by the World Health Organization and the Turkish Standard. Because water from the River Buyukmelen will be used as drinking water, it will have an adverse effect on water quality and humans if not treated in advance. In addition, the inclusion of Mn and Zn in the Elmali drinking‐water reservoir of Istanbul and Fe in the River Buyukmelen water indicates natural inorganic contamination. Mn, Zn and Fe contents in the waters are related to geological origin. Moreover, the River Buyukmelen flow is very muddy in the rainy seasons and it is inevitable that this will pose problems during the purification process. Copyright © 2005 John Wiley & Sons, Ltd.     

Chemical variations of tephra-fall deposit leachates for three eruptions from Popocatépetl volcano

Leachates from ash samples of the Popocatépetl eruptions of April 30, 1996, May 12, 1997, and October 17, 1998 settled at different distances from the crater were analyzed for anions (SO₄²⁻, Cl⁻, F⁻) and some metals. This study is aimed at determining the causes of the compositional variations of the leachates, to assist the assessment of water, soil and crop contamination due to ash deposits. Different behavior was observed in the ion concentrations with distance for the three eruptions. On April 30, 1996, SO₄²⁻ and F⁻ concentrations increased with distance, and Cl⁻ remained almost constant. On May 12, 1997, concentrations of the three anions decreased with distance. On October 17, 1998, F⁻, Cl⁻ and SO₄²⁻ increased more than three-fold with distance. Tephra size distributions were also different for the three eruptions. The observed trends of the leachates’ anion concentrations may have different causes: the type and intensity of the eruptions, the distribution of the tephra sizes, the degree of interaction of the tephras with volcanic gases, humidity, static charge, the original characteristics of the solid material, the transport time from the crater to the site of settling, and the relative angle between the wind direction and the sampling line. Enrichment factors and concentration trends for metals with distance suggest that Co, Ni, Cu and Pb in the leachates resulted mostly from volcanic gas adsorption.     

Analytical laboratory comparison of major and minor constituents in an active crater lake

The crater lake water from Maly Semiachik volcano in Kamchatka was used for the international analytical laboratory comparison of major and minor elements, and hydrogen, sulfur, and oxygen isotope data. Eight institutions participated in this program, giving analytical results of 9 major and 20 minor elements mainly by using ICP-AES for cations and IC for anions. Among the major elements, Na, Mg and Si showed coefficients of variation (CV) of 10% or more, whereas B, Al, Fe, Mn had coefficients less than 7%. The CV% of the minor elements Co, Cu, P, Cr, Pb was much greater (>30%) while the V analyses agreed well (<10%). Ti, Sr, Zn, and F were intermediate (between 10 and 20 CV%). The errors observed for these constituents are inherent to the methods applied: large dilutions and spectrometric interferences. Even the major anions such as Cl (>2000 ppm) and SO₄ (>5000 ppm) gave considerable ranges (5.1 and 8.8 CV%, respectively) as did the obtained pH values (22 CV%). The measured δ¹⁸O of the water samples and δ³⁴S of sulfate are in excellent agreement but the δD values had CV% of 8. Technical recommendations are presented to improve the analytical results for these elements with significant deviations from the mean values.     

Isotopic geochemistry of acid thermal waters and volcanic gases from Zaō volcano in Japan

The chemical composition and D/H, and ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO₂, SO₂ and N₂, exclusive of H₂O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ³⁴S values of around +15‰, are enriched in ³⁴S compared to Zaō H₂S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ³⁴S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ³⁴S than those of other volcanic areas, reflecting the difference in total pressure.     

Chemical characteristics of the crater lakes of Popocatetetl, El Chichon, and Nevado de Toluca volcanoes, Mexico

Three crater lakes from Mexican volcanoes were sampled and analyzed at various dates to determine their chemical characteristics. Strong differences were observed in the chemistry among the three lakes: Nevado de Toluca, considered as dormant, El Chichón at a post-eruptive stage, and Popocatépetl at a pre-eruptive stage. Not surprisingly, no influence of volcanic activity was found at the Nevado de Toluca volcano, while the other volcanoes showed a correlation between the changing level of activity and the evolution of chemical trends. Low pHs (<3.0) were measured in the water from the active volcanoes, while a pH of 5.6 was measured at the Nevado de Toluca Sun lake. Changes with time were observed at Popocatépetl and El Chichón. Concentrations of volcanic-gas derived species like Cl⁻, SO₄²⁻ and F⁻ decreased irregularly at El Chichón from 1983 until 1997. Major cations concentrations also diminished at El Chichón. A 100% increase in the SO₄²⁻ content was measured at Popocatépetl between 1985 and 1994. An increase in the Mg/Cl ratio between 1992 (Mg/Cl=0.085) and 1994 (Mg/Cl=0.177) was observed at Popocatépetl, before the disappearance of the crater lake in 1994. It is concluded that chemical analysis of crater lakes may provide a useful additional tool for active-volcano monitoring.     

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.     

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO₂ concentrations reached 1000 mg/kg in the lower stratum. Loss of CO₂ from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO₄ and HCO₃ contents of Lake Quilotoa are intermediate between those of acid–SO₄–Cl Crater lakes and those of neutral-HCO₃ Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO₄–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO₂ (3×10¹¹ g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO₂-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.     

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.     

Radionuclides and sulfur content in Mount Etna plume in 1983–1995: new constraints on the magma feeding system

Radionuclide activities (²¹⁰Pb, ²¹⁰Bi, ²¹⁰Po) were investigated in Mount Etna plume from 1983 to 1995. At SE crater the long-term observation (12 years) of the ²¹⁰Po/²¹⁰Pb ratio shows that it can behave as a degassing vent not directly related to the main magma reservoir depending on the magma level inside the volcano. Since 1992, the simultaneous determination of radionuclides and sulfur in the main plume results in new constraints on the degassing model of Lambert et al. (Earth Planet. Sci. Lett., 76 (1986) 185). The ²¹⁰Po/SO₂ and ²¹⁰Pb/SO₂ ratios enable us to identify two sources of ²¹⁰Po in the plume: one is magmatic, correlated with SO₂, the other one is an additional component issued from the decay of ²¹⁰Pb in the shallow degassing cell, and depends directly on the residence time of the gases before their emission. Estimations of the volume of degassing magma, the residence time of the gases and the proportion of undegassed magma renewing the shallow degassing cell are given for the period 1992–1995. During the 1992 eruption, the rate of degassing magma volume is estimated to have been as high as 5×10⁶ m³/day, and the volume of the shallow degassing magma reservoir about 0.5 km³. In 1994 and 1995 the rate of non-erupted degassing magma volume was estimated to have been about 0.18 km³/year. During the entire 1983–1995 period, only 15–20% of the degassed magma was erupted.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Using Crater Lake chemistry to predict volcanic activity at Poás Volcano,Costa Rica

Monitoring of crater lake chemistry during the recent decline and disappearance of the crater lake of Poás Volcano revealed that large variations in SO₄/Cl, F/Cl, and Mg/Cl ratios were caused by the enhanced release of HCl vapor from the lake surface due to increasing lake temperature and solution acidity. Variation in the concentration of polythionic acids (H₂S_xO₆, x=4–6) was the most reliable predictor of renewed phreatic eruptive activity at the volcano, exhibiting sharp decreases three months prior to the initiation of phreatic eruptions in June 1987. Polythionic acids may offer a direct indicator of changing subsurface magmatic activity whereas chloride-based element ratios may be influenced by surface volatilization of HCl and subsequent recycling of acidic fluids in crater lake volcanoes.     

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.