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.     

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.     

The behaviour of metals and sulphur during the formation of hydrothermal mercury–antimony–arsenic mineralization, Uzon caldera, Kamchatka, Russia

Uzon caldera, located in the eastern volcanic belt of the Kamchatka peninsula, is a complicated structure of Middle Pleistocene age. The composition of the co-existing solid and fluid phases, temperature and pH were determined with the aim of establishing the distribution of sulphur species, As, Sb and the main ore-forming metals. In the solid samples, the following sulphur-bearing minerals were identified: pyrite, realgar, orpiment, alacranite (As₈S₉), uzonite (As₄S₅), amorphous As-sulphide, stibnite, cinnabar and native sulphur. The following sulphur-bearing species H₂S, H₂S₂+S₅²⁻(aq)(aqueous polysulphanes), S⁰(aq), SO₃²⁻(aq), S₂O₃²⁻, SO₄²⁻ and total concentration of sulphur were determined in solutions. Eh, pH and H₂S concentration were measured potentiometrically in situ. Zero-valent sulphur (S⁰(aq)+H₂S₂+S₅²⁻(aq)) predominates in Uzon solutions. The pair H₂S–S_colloidal is Eh-determining in Uzon solutions up to 75–85°C. A quantitative thermodynamic model of the mineral deposition process at Uzon was constructed using the collected data. It was obtained that the composition of the hydrothermal solution and the precipitation of Sb–As–Hg species can be described using two only main factors: the initial composition of fluid and the temperature variation.     

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.     

Airborne measurements of particle and gas emissions from the December 1994–January 1995 eruption of Popocatépetl volcano (Mexico)

Airborne and ground-based (correlation spectrometer, cascade impactor, and photoelectric counter together with intake filter probes) measurements are described for the volcanic emissions from Popocatépetl volcano (Mexico) from December 23, 1994 to January 28, 1995. Measurements of SO₂ restarted 48 h after the eruption onset of December 21, 1994. Maximum sulfur dioxide (4560 t d⁻¹) plus 3.8×10⁴ t d⁻¹ of particulate matter were ejected on December 24, 1994. The maximum rate of ejection occurred coincidentally with the maximum amplitude of harmonic tremor and the maximum number of seismic type B events. Sulfur dioxide emission rates ranged from 1790 to 2070 t d⁻¹ (December 23–24, 1994). Afterwards, sulfur dioxide emission rates clearly indicated a consistent decline. However, frequent gas and ash emission puffs exhibited SO₂ fluxes reaching values as high as 3060 t d⁻¹. The emission SO₂ baseline for the period of study (February 1994–January 1995) was about 1000 t d⁻¹. Ejection velocity of particulate matter was approximately 270 m s⁻¹ reaching a height of about 2.5 km over the summit. The immediate aerosol dispersion area was estimated at 6.0×10⁴ km² maximum. The microscopic structure of particles (aerosol and tephra) showed a fragile material, probably coming from weathered crustal layers. X-ray fluorescence and neutron-activation analysis from the impactor samples found the following elements: Si, Al, Ca, S, P, Cl, K, Ni, Fe, Ti, Sc, Cu, Zn, Mn, Sr, Cr, Co, Y, Br, Se, Ga, Rb, Hg and Pb. Morphological analysis shows that ash samples might be from pulverized basaltic rock indicating that the Popocatépetl eruption of December 21, 1994 was at low temperature. The microscopic structure of puff material showed substance aggregates consisted of fragile rock, water and adsorbed SO₂. These aggregates were observed within water droplets of approximately 1 mm and even larger. Sulfur transformations in the droplets occurred intensively. Volcanic ash contained 5–6% of sulfur during the first expulsion hours. Elemental relative concentrations with respect to Al show that both Si and S have relative concentrations >1, i.e., 13.73 and 2.17, respectively in agreement with the photoelectric counter and COSPEC measurements.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

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.     

Evaluation of volcanic gas analysis from surtsey volcano, iceland 1964–1967

Methods used previously to remove compositional modifications from volcanic gas analyses for Mount Etna and Erta'Ale lava lake have bean employed to estimate the gas phase composition at Nyiragongo lava lake, based on samples obtained in 1959. H₂O data were not reported in 11 of the 13 original analyses. The restoration methods have been used to estimate the H₂O contents of the samples and to correct the analyses for atmospheric contamination, loss of sulfur and for pre- and pest-collection oxidation of H₂S, S₂, and H₂. The estimated gas compositions are relatively CO₂-rich, low in total sulfur and reduced. They contain approximately 35–50% CO₂ 45–55% H₂O, 1–2% SO₂, 1–2% H₂., 2–3% CO, 1.5–2.5% H₂S, 0.5% S₂ and 0.1% COS over,he collection temperature range 102° to 960° C. The oxygen fugacities of the gases are consistently about half an order of magnitude below quartz-magnetite-fayalite. The low total sulfur content and resulting low atomic S/C of the Nyiragongo gases appear to be related to the relatively low f_O2 of the crystallizing lava. At temperatures above 800°C and pressures of 1–1.5 k bar, the Nyiragongo gas compositions resemble those observed in primary fluid inclusions believed to have formed at similar temperatures and pressures in nephelines of intrusive alkaline rocks. Cooling to 300°C, with f_O2 buffered by the rock, results in gas compositions very rich in CH₄ (50–70%) and resembling secondary fluid inclusions formed at 200–500°C in alkaline rocks. Below 600°C the gases become supersaturated in carbon as graphite. These inferences are corroborated by several reports of hydrocarbons in plutonic alkaline rocks, and by the presence of CH₄-rich waters in Lake Kivu — a lake on the flanks of Nyiragongo volcano.     

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.     

Composition of back-arc basin volcanics, Valu Fa Ridge, Lau Basin: Evidence for a slab-derived component in their mantle source

Samples dredged from 2 localities near the crest of the Valu Fa ridge, an active back-arc basin spreading centre in the Lau Basin, consist of highly vesicular lava fragments of andesitic composition. The samples are characterized by rare, euhedral An₈₅ plagioclase phenocrysts in a hypocrystalline groundmass of An₆₀ plagioclase laths, brown glass and rare subhedral clinopyroxene. Samples from within and, to a lesser extent, between the dredge hauls show remarkable isotopic and chemical homogeneity, with: ⁸⁷Sr/⁸⁶Sr − 0.70330 ± 2; ¹⁴³Nd/¹⁴⁴Nd − 0.51303 ± 2; ²⁰⁶Pb/²⁰⁴Pb − 18.65 ± 2; ²⁰⁷Pb/²⁰⁴Pb − 15.55 ± 1; ²⁰⁸Pb/²⁰⁴Pb − 38.34 ± 4; Sr − 165 ppm; Rb − 7 ppm; Cs − 0.17 ppm; K − 3300 to 4200 ppm; Ba − 96 ppm; and REE — LREE depleted with 12–18 × chondritic abundances. On Sr-Nd, Pb-Pb and Sr-Pb plots the volcanics lie just within or on the edge of the MORB fields, overlapping with island-arc volcanics from the Marianas and Tonga. Compared with MORB and ocean-island basalts, the samples show alkali-element enrichment relative to REE and higher Cs relative to Rb. The isotopic and geochemical characteristics of the Valu Fa Ridge volcanics clearly indicate a minor, but significant, slab-derived component in the back-arc basin mantle source.     

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.     

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 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.     

Lake Koronia, Greece: Shift from autotrophy to heterotrophy with cultural eutrophication and progressive water-level reduction

Lake Koronia, a Ramsar site, is shallow, polymictic, hypertrophic and until recently was aerially the fourth largest lake in Greece. Although exceeding 5 m in the past, lake depth has declined progressively from 3.8 m in 1980 to < 1 m in 1997, reducing surface area and water volume by 50% and 80%, respectively. Specific conductivityincreased from 1300 μS cm⁻¹ in 1977 to >6000 μS cm⁻¹ in 1991. Increased phosphate concentrations from the late 1970's (8–45 μg L⁻¹) to the late 1990's (100–1000 μg L⁻¹) document that the previously eutrophic system with a limited littoral zone switched to hypertrophy dominated by massive cyanobacteria blooms. Oxygen saturation of the water column increased progressively from about 80% in 1983 to full saturation about 1993, after which it decreased progressively to only 20% saturation in 1997. In spite of cyanobacteria dominance, community metabolism of the lake switched from progressively increasing autotrophy to rapidly advancing heterotrophy associated with progressive water-level reduction leading to fish extirpation in the lake.     

A hydrobiological study to interpret the presence of desmids in Lake Zirahuén, México

Monthly collections of phytoplankton were supported by physical–chemical data and measures of chlorophyll a concentrations in the search for particular environmental factors that could explain the constant presence of desmids in a Mexican tropical lake, a characteristic not common among the phytoplanktic communities of Mexican lakes. Samplings were taken from the water column in the deepest part of the lake (40 m) and intensified in the metalimnetic zone, whose establishment was monitored by observations of temperature and oxygen profiles. The general behavior of Lake Zirahuén was typical of warm monomictic tropical lakes at high elevation: a short mixing phase during the hemispheric winter. The depth of Z_MIX and Z_eu revealed a well-illuminated epilimnion, suggesting that phytoplankton communities are not likely to be light-limited. The oligotrophic nature of the lake is indicated by discrete concentrations of inorganic nutrients, P_TOT in the interval of 0.01–0.03 mg l⁻¹ and chlorophyll a between 0.23 and 3.98 μg l⁻¹. These characteristics together with a low concentration of calcium, define a lacustrine environment different from other Mexican lakes, and one that could be suitable for desmids communities.     

Fumaroles in ice caves on the summit of Mount Rainier—preliminary stable isotope, gas, and geochemical studies

The edifice of Mount Rainier, an active stratovolcano, has episodically collapsed leading to major debris flows. The largest debris flows are related to argillically altered rock which leave areas of the edifice prone to failure. The argillic alteration results from the neutralization of acidic magmatic gases that condense in a meteoric water hydrothermal system fed by the melting of a thick mantle of glacial ice. Two craters atop a 2000-year-old cone on the summit of the volcano contain the world's largest volcanic ice-cave system. In the spring of 1997 two active fumaroles (T=62°C) in the caves were sampled for stable isotopic, gas, and geochemical studies.Stable isotope data on fumarole condensates show significant excess deuterium with calculated δD and δ¹⁸O values (−234 and −33.2‰, respectively) for the vapor that are consistent with an origin as secondary steam from a shallow water table which has been heated by underlying magmatic–hydrothermal steam. Between 1982 and 1997, δD of the fumarole vapor may have decreased by 30‰.The compositions of fumarole gases vary in time and space but typically consist of air components slightly modified by their solubilities in water and additions of CO₂ and CH₄. The elevated CO₂ contents (δ¹³C_CO2=−11.8±0.7‰), with spikes of over 10,000 ppm, require the episodic addition of magmatic components into the underlying hydrothermal system. Although only traces of H₂S were detected in the fumaroles, most notably in a sample which had an air δ¹³C_CO2 signature (−8.8‰), incrustations around a dormant vent containing small amounts of acid sulfate minerals (natroalunite, minamiite, and woodhouseite) indicate higher H₂S (or possibly SO₂) concentrations in past fumarolic gases.Condensate samples from fumaroles are very dilute, slightly acidic, and enriched in elements observed in the much higher temperature fumaroles at Mount St. Helens (K and Na up to the ppm level; metals such as Al, Pb, Zn Fe and Mn up to the ppb level and volatiles such as Cl, S, and F up to the ppb level).The data indicate that the hydrothermal system in the edifice at Mount Rainier consists of meteoric water reservoirs, which receive gas and steam from an underlying magmatic system. At present the magmatic system is largely flooded by the meteoric water system. However, magmatic components have episodically vented at the surface as witnessed by the mineralogy of incrustations around inactive vents and gas compositions in the active fumaroles. The composition of fumarole gases during magmatic degassing is distinct and, if sustained, could be lethal. The extent to which hydrothermal alteration is currently occurring at depth, and its possible influence on future edifice collapse, may be determined with the aid of on site analyses of fumarole gases and seismic monitoring in the ice caves.     

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     

Authigenic carbonates in sediments from the Gulf of Mexico

The carbon isotopic composition of diagenetic dolomite and calcite in some sediments of the Gulf of Mexico varies between “normal-marine” (δ¹³C ca. 0‰) and −14.6‰ which suggests that biogenic CO₂ contributed to the carbonate formation. The δ¹³O values of dolomite and coexisting calcite are very similar but variable down-core.Dolomite and calcite precipitated early from pore water where SO₄²⁻ was not reduced. However, during (and after?) SO₄²⁻ reduction dolomite and calcite still formed and there are at least two generations of carbonate minerals present.     

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.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. II. Formation and decomposition of thiosulfate and polythionate in Cinder Pool

Cinder Pool is an acid-sulfate-chloride boiling spring in Norris Geyser Basin, Yellowstone National Park. The pool is unique in that its surface is partially covered with mm-size, black, hollow sulfur spherules, while a layer of molten sulfur resides at the bottom of the pool (18 m depth). The sulfur speciation in the pool was determined on four different days over a period of two years. Samples were taken to evaluate changes with depth and to evaluate the importance of the sulfur spherules on sulfur redox chemistry. All analyses were conducted on site using a combination of ion chromatography and colorimetric techniques.Dissolved sulfide (H₂S), thiosulfate (S₂O₃²⁻), polythionates (S_xO₆²⁻), and sulfate were detected. The polythionate concentration was highly variable in time and space. The highest concentrations were found in surficial samples taken from among the sulfur spherules. With depth, the polythionate concentrations dropped off. The maximum observed polythionate concentration was 8 μM. Thiosulfate was rather uniformly distributed throughout the pool and concentrations ranged from 35 to 45 μM. Total dissolved sulfide concentrations varied with time, concentrations ranged from 16 to 48 μM. Sulfate was relatively constant, with concentrations ranging from 1150 to 1300 μM. The sulfur speciation of Cinder Pool is unique in that the thiosulfate and polythionate concentrations are significantly higher than for any other acid-sulfate spring yet sampled in Yellowstone National Park. Complementary laboratory experiments show that thiosulfate is the intermediate sulfoxyanion formed from sulfur hydrolysis under conditions similar to those found in Cinder Pool and that polythionates are formed via the oxidation of thiosulfate by dissolved oxygen. This last reaction is catalyzed by pyrite that occurs as a minor constituent in the sulfur spherules floating on the pool's surface. Polythionate decomposition proceeds via two pathways: (1) a reaction with H₂S, yielding thiosulfate and elemental sulfur; and (2) by disproportionation to sulfate and thiosulfate.This study demonstrates that the presence of a subaqueous molten sulfur pool and sulfur spherules in Cinder Pool is of importance in controlling the pathways of aqueous sulfur redox reactions. Some of the insights gained at Cinder Pool may be relevant to acid crater lakes where sulfur spherules are observed and variations in polythionate concentrations are used to monitor and predict volcanic activity.