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.     

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.     

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.     

Volcanic lake systematics I. Physical constraints

 Volcanic lakes have a wide range of characteristics, and we make an attempt to delineate the limiting physical conditions for several lake classes. The ratio between heat input and heat dissipation capacity of a lake constrains the temperature for perfectly mixed steady-state volcanic lakes. Poorly mixed lakes are also conditioned by this ratio, but their temperature structure is also strongly influenced by the hydrodynamics resulting from different mechanisms of heat transfer. The steady-state temperatures of volcanic lakes are largely determined by the magnitude of the volcanic heat influx relative to the surface area of the lake. Small lakes have only a small capacity for heat dissipation and their temperature rises quickly with only small heat inputs; large lakes are buffered against variations in heat input. Both the heat dissipation and meteoric water input into a lake are functions of lake surface area and therefore each lake water temperature demands a certain precipitation rate for mass conservation, independent of lake size. The results of energy/mass-balance modeling shows that under common atmospheric conditions, most steady-state volcanic lakes are unlikely to maintain a temperature in excess of 45–50  °C. Validation of the volcanic lake model was performed using published data from Yugama Lake (Japan) and the Keli Mutu lakes (Indonesia). Also, the model was applied to 24 natural systems to provide a baseline assessment of energy fluxes under the model assumptions so future work on those systems can identify nuances in individual systems that deviate from the simple model conditions. We recommend the model for use in assessing temperature variations and volcanic lake stability in settings with known physical and atmospheric conditions. Application of the energy/mass balance calculations of model lakes provides a genetic classification scheme largely based on physical process parameters. Received: 28 February 1996 / Accepted: 23 November 1996     

Chemical and stable isotopic models for boundary creek warm springs, southwestern Yellowstone National Park, Wyoming

Thermal springs of the Boundary Creek hydrothermal system in the southwestern part of Yellowstone Park outside the caldera boundary vary in chemical and isotopic composition, and temperature. The diversity may be accounted for by a combination of processes including boiling of a deep thermal water, mixing of the deep thermal water with cool meteoric water and/or with condensed steam or steam-heated meteoric water, and chemical reactions with surrounding rocks. Dissolved-silica, Na⁺, K⁺ and Ca²⁺ contents of the thermal springs could result from a thermal fluid with a temperature of 200 ± 20°C. Chloride-enthalpy and silica-enthalpy mixing models suggest mixing of 230°C, 220 mg/l Cl⁻ thermal water with cool, low-Cl⁻ components. A 350 to 390°C component with Cl⁻ ≥ 300 mg/l is possibly present in thermal springs inside the caldera but is not required to fit observed spring chemical and isotopic compositions. Irreversible mass transfer models in which a low-temperature water reacts with volcanic glass as it percolates downward and warms, can account for observed pH and dissolved-silica, K⁺, Na⁺, Ca²⁺ and Mg²⁺ concentrations, but produces insufficient Cl⁻ or F⁻ for measured concentrations in the warm springs. The ratio of a_Na/a_H, and Cl⁻ are best accounted for in mixing models. The water-rock interaction model fits compositions of acid-sulfate waters observed at Summit Lake and of low-Cl⁻ waters involved in mixing.The cold waters collected from southwestern Yellowstone Park have δD values ranging from −118 to −145 per mil and δ¹⁸O values of −15.9 to −19.4 per mil. Two samples from nearby Island Park have δD values of −112 and −114 per mil and δ¹⁸O values of −15.1 and −15.3 per mil. All samples of thermal water plot significantly to the right of the meteoric water line. The low Cl⁻ and variable δD values of the thermal waters indicate isotopic compositions are derived by extensive dilution with cold meteoric water and by steam separation on ascent to the surface. Many of the hot springs with higher δD values may contain in addition a significant amount of high-D, low-Cl⁻, acid-sulfate or steam-heated meteoric water. Mixing models, Cl⁻ content and isotopic compositions of thermal springs suggest that 30% or less of a deep thermal component is present. For example, the highest-temperature springs from Three Rivers, Silver Scarf and Upper Boundary Creek thermal areas contain up to 70% cool meteoric water and 30% hot water components, springs at Summit Lake and Middle Boundary Creek spring 57 are acid-sulfate or steam-heated meteoric water; springs 27 and 48 from Middle Boundary Creek and 49 from Mountain Ash contain in excess of 50% acid-sulfate water; and Three Rivers spring 46 and Phillips could result from mixing hot water with 55% cool meteoric water followed by mixing of acid-sulfate water. Extensive dilution by cool meteoric water increases the uncertainties in quantity and nature of the deep meteoric, thermal component.     

Chemical and isotopic signatures of the basement rocks from the Campi Flegrei geothermal field (Naples, southern Italy): inferences about the origin and evolution of its hydrothermal fluids

The Campi Flegrei (Naples, Campanian Plain, southern Italy) geothermal system is hosted by Quaternary volcanic rocks erupted before, during and after the formation of the caldera that represents one of the major structural features in the Neapolitan area. The volcanic products rest on a Mesozoic carbonate basement, cropping out north, east and south of the area. Chemical (major, minor and trace elements) and stable isotope (C, H, O) analyses were conducted on drill-core samples recovered from geothermal wells MF-1, MF-5, SV-1 and SV-3, at depths of ˜ 1100 to 2900 m. The study was complemented by petrographic and SEM examination of thin sections. The water which feeds the system is both marine and meteoric in origin. Mineral zonation typical of a high-temperature geothermal system exists in all the geothermal wells; measured temperatures in wells are as high as ˜ 400 °C. The chemical composition of the waters suggests the existence of two reservoirs: a shallow reservoir (depth < 2000 m) fed by seawater that boiled at 320 °C and became progressively diluted by steam-heated local meteoric water during its ascent; and a deeper reservoir (depth > 2000 m) of hypersaline water. The drill-cores are mainly hydrothermally altered volcanics of trachy-latitic affinity, but some altered pelites and limestones are also present. Published Na, Mg and K concentrations of selected geothermal waters indicate that the hydrothermal fluids are in equilibrium with their host rocks, with respect to K-feldspar, albite, sericite and chlorite. The measured δ¹⁸O_(SMOW) values of rocks range from +4.3 to + 16.5%. The measured δD_(SMOW) values range from − 79 to − 46%. The calculated isotopic composition of the fluids at equilibrium with the samples vary from + 1 to + 8.3%. δ¹⁸O and from − 52 to + 1%. δD. The estimated isotopic composition of the waters at equilibrium with the studied samples confirmed the existence of two distinct fluid types circulating in the geothermal system. The shallower has a marine water signature, while the deeper water has a signature consistent both with magmatic and meteoric origins. In the latter case, the recharge of this aquifer likely occurs at the outcrop of the Mesozoic Limestones surrounding the Campanian Plain; after infiltration, the water percolates through evaporitic layers, becoming hypersaline and D-depleted.     

D/H and O/O ratios of water in the crater lake at Kusatsu-Shirane volcano, Japan

The D/H and ¹⁸O/¹⁶O ratios of water in the active crater lake situated on the Kusatsu-Shirane volcano, Japan are about 20 and 6‰, respectively, higher than local meteoric water. The ratios show seasonal variations superimposed on a gradual change over nine years. The isotopic ratios started to increase in early 1990 and decrease in the spring of 1995. The seasonal variation which is high in winter and low in summer correlates with the temperature difference between lake water and ambient air. The large temperature difference in winter enhances the evaporation of lake water and produces the enriched isotopic ratios relative to the ratios in summer. The accumulation of snow and the decrease in the flux of meteoric water into the lake strengthens the winter-time isotopic enrichment. The enriched isotopic ratios of the lake water over a long time result from the addition of an end member with heavy isotopic ratios contained in a thermal fluid supplied to the lake. Considering the water balance in the lake, the isotopic ratios of the thermal fluid were found to be close to the lake water itself, suggesting the circulation of the lake water seeping through lake floor. Based on the correlation between Cl⁻concentration and the isotopic ratios, the contribution by the heavy end member was estimated to be 25–36% relative to the enrichment by evaporation. The heavy end member could be a liquid phase evolved from a parental fluid, which is a mixture of local meteoric water and a magmatic fluid as found in high-temperature volcanic gases.     

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.     

Sr isotope diversity of hot spring and volcanic lake waters from Zao volcano,Japan

The ratio of ⁸⁷Sr/⁸⁶Sr was measured from different water samples of thermal/mineral (hot spring as well as crater lake) and meteoric origins, in order to specify the location and to verify the detailed model of a volcano-hydrothermal system beneath Zao volcano. The ratio showed a trimodal distribution for the case of thermal/mineral water: 0.7052–0.7053 (Type A, Zao hot spring), 0.7039–0.7043 (Type B, Okama crater lake and Shin-funkiko hot spring), and 0.7070–0.7073 (Type C, Gaga, Aone, and Togatta hot springs), respectively. However, in comparison, the ratio was found to be higher for meteoric waters (0.7077–0.7079). The water from the central volcanic edifice (Type B) was found to be similar to that of nearby volcanic rocks in their Sr isotopic ratio. This indicates that the Sr in water was derived from shallow volcanic rocks. The ⁸⁷Sr/⁸⁶Sr ratio for water from the Zao hot spring (Type A) was intermediate between those of the pre-Tertiary granitic and the Quaternary volcanic rocks, thus suggesting that the water had reacted with both volcanic and granitic rocks. The location of the vapor–liquid separation was determined as the boundary of the pre-Tertiary granitic and the Quaternary volcanic rocks by comparing the results of this strontium isotopic study with those of Kiyosu and Kurahashi [Kiyosu, Y., Kurahashi, M., 1984. Isotopic geochemistry of acid thermal waters and volcanic gases from Zao volcano in Japan. J. Volcanol. Geotherm. Res. 21, 313–331.].     

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.     

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.     

Oxygen isotopic composition of alkaline anorogenic granites as a clue to their origin: the problem of crustal oxygen

The primary isotopic characteristics of alkaline granites are often obscured by secondary processes enhanced by their unusual chemical compositions. This is true for radiogenic as well as for stable isotopes. For example, the ⁸⁷Sr/⁸⁶Sr ratios can vary drastically in closed systems because of very high Rb/Sr ratios and can also be easily modified by direct or indirect interaction with continental crust because of low Sr concentrations. Moreover, the frequent occurrence of the granitic massifs as hypovolcanic complexes increases the probability of interaction with meteoric waters which is a common source of important isotopic variability.The investigation of oxygen isotope systematics in alkaline acidic rocks from various environments shows the¹⁸O content of their quartz to be highly invariable, and the δ¹⁸O values to be close to the mantle range of values. This is due to the resistance of quartz to isotopic exchange, which makes it a good tracer of primary isotopic composition. If we eliminate the quartz δ¹⁸O values for which interaction with meteoric water is well documented (five samples), the total range of variation (seventeen samples) is from 6.0 to 7.3‰ relative to SMOW. The values can easily be accounted for by, and correspond to, equilibrium with mantle-type material in a temperature range of 1200-800°C. If we consider possible effects of fractional crystallization, this temperature range can probably be reduced to its lower limit which is much more likely for rocks of acidic composition.The present oxygen isotope study strongly supports an origin for alkaline anorogenic granites from mantle-dominated sources.     

A stable isotope study of the Garda lake, northern Italy: Its hydrological balance

Discontinuous measurements of the isotopic composition of surface water samples of the Garda lake carried out between 1998 and 2006 showed almost constant δ¹⁸O, δD and d-excess values through time. During 2006 and 2007 monthly vertical profiles of water samples were collected in the northernmost section of the lake, not far from the main inflow (Sarca river) to check whether there was any detectable influence from this inflowing river and whether there was a vertical isotopic stratification of the lake water. The isotopic measurement of water samples from the vertical profiles yielded isotopic values which were almost equal to those obtained from surface waters showing no detectable effect of the inflowing river water and no isotopic vertical stratification. The attempt to evaluate the evaporation rate of lake water by means of current models was totally unsuccessful. Despite the marked summer warming of the surface layer no isotopic fractionation related to evaporation processes could be detected. This anomalous behaviour may be related to the large amount of spring and summer precipitation characteristic of this area. The water balance of the lake calculated according to the amount of the inflowing water (Sarca river water plus rain water on the lake plus 20% of the precipitations on the whole catchment basin) and to the amount of outflowing water (Mincio river) showed a large imbalance, the river outflow alone resulting on average, during the last decade, at least double the inflow. To explain this imbalance of the lake, a large recharge by concealed groundwater is suggested: its isotopic composition should be quite close to the mean isotopic composition of precipitations over that area. This would be in agreement with the almost constant isotopic composition of both surface and deep waters and with the lack of vertical isotopic stratification. A few measurements of the tritium concentration carried out on lake water show values that are considerably higher than modern tritium values either in precipitation or in the Sarca river water: these results are in good agreement with the hypothesis of a recharge of the lake by deep aquifers.     

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     

Tritium and stable isotopes of magmatic waters

To investigate the isotopic composition and age of water in volcanic gases and magmas, we analyzed samples from 11 active volcanoes ranging in composition from tholeiitic basalt to rhyolite: Mount St. Helens (USA), Kilauea (USA), Pacaya (Guatemala), Galeras (Colombia), Satsuma Iwo-Jima (Japan), Sierra Negra and Alcedo (Ecuador), Vulcano (Italy), Parícutin (Mexico), Kudryavy (Russia), and White Island (New Zealand). Tritium at relatively low levels (0.1–5 T.U.) is found in most emissions from high-temperature volcanic fumaroles sampled, even at discharge temperatures >700°C. Although magmatic fluids sampled from these emissions usually contain high CO₂, S_total, HCl, HF, B, Br, ³He R/R_A, and low contents of air components, stable isotope and tritium relations of nearly all such fluids show mixing of magmatic volatiles with relatively young meteoric water (model ages≤75 y). Linear δD/δ¹⁸O and ³H/δ¹⁸O mixing trends of these two end-members are invariably detected at arc volcanoes. Tritium is also detected in fumarole condensates at hot spot basalt volcanoes, but collecting samples approaching the composition of end-member magmatic fluid is exceedingly difficult. In situ production of ³H, mostly from spontaneous fission of ²³⁸U in magmas is calculated to be <0.001 T.U., except for the most evolved compositions (high U, Th, and Li and low H₂O contents). These values are below the detection limit of ³H by conventional analytical techniques (about 0.01 T.U. at best). We found no conclusive evidence that natural fusion in the Earth produces anomalous amounts of detectable ³H (>0.05 T.U.).     

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.     

Water–Rock interactions in the basement beneath Long Valley Caldera: an oxygen isotope study of the Long Valley Exploratory Well drill cores

The Long Valley Exploratory Well, at the center of the Resurgent Dome of Long Valley caldera, penetrated pre-caldera basement rocks at a depth of 2101.72–2313.0 m, beneath the caldera-forming Bishop Tuff and post-caldera Early Rhyolite. The basement rocks contain prominent quartzites, with ubiquitous milky white quartz veins (with minor calcite and pyrite) and fractures of varied orientation and geometry. The other members of the basement sequence are very fine-grained quartz-rich graphitic pelites with calcite veins, spotted hornfels, and shallow intrusive rocks. Previous studies established the presence of a post-caldera, paleohydrothermal system (500–100 ka) to a depth of 2000 m that affected the Bishop Tuff and a recent (40 ka to present) hydrothermal system at shallow depth (<1 km). The deeper extent of these hydrothermal activities is established in this paper by a detailed oxygen isotope analysis of the drill core samples. 238 analyses of δ¹⁸O in 50 quartz veins within the 163.57 m depth interval of basement rocks reveal extreme heterogeneity in δ¹⁸O values (8–19.5‰). Majorities of the 84 bulk analyses of quartzites show variation of δ¹⁸O within a narrow range of 14–16‰. However, certain samples of these quartzites near the contacts with veins and fractures exhibit sharp drops in δ¹⁸O. The interbedded pelitic rocks and spotted hornfels have whole-rock δ¹⁸O ranging from 2.2 to 11.8‰. Clear, euhedral vuggy quartz that partially fills earlier open fractures in both the quartzites and quartz veins, has distinctive δ¹⁸O, ranging between −3.2 and +8.4‰. Low values of δ¹⁸O are also found in the hydrothermal minerals and whole rocks adjacent to the thin veins, clearly indicating infiltration of meteoric water. Three distinct observed patterns of fractionation in δ¹⁸O between veins and host quartzites are analyzed with the principles of mass balance, equilibrium oxygen isotope fractionation in closed system, and kinetically controlled oxygen isotope exchange in an open system. This analysis suggests that the early quartz veins formed due to a magmatic-hydrothermal activity with no influx of external water once the system comprising the sedimentary envelope and a magmatic-hydrothermal fluid phase became closed. Two-stage isotopic exchange processes caused fractionation in the δ values that originally formed arrays with slope 1 in a δ_{vein quartz}–δ_{host quartzite} space. Another array in the same space, with near zero slope was also formed due to variation in temperature, initial isotopic compositions of the quartzite sequence and the fluid phase. Variation in temperature was mostly in the range of 300–400°C giving Δ (=δ_{vein quartz}–δ_{host quartzite})≈−2.8 to +2.8. The δ¹⁸O of the fluid could range from −5 to +10; however a narrower range of +5 to +10 can explain the data. This episode of hydrothermal activity could take place either as a single pulse or in multiple pulses but each as a closed system. A later, fracture-controlled, meteoric water (δ¹⁸O−0.46 to −12.13) flow and interaction (at 250°C) is interpreted from the analysis of δ¹⁸O values of the coexisting quartz and calcite pairs and existence of markedly ¹⁸O-depleted pelitic horizons interbedded with ¹⁸O-enriched quartzite layers. Thus, the interpreted earlier magmatic-hydrothermal activity was overprinted by a later meteoric-hydrothermal activity that resulted in steep arrays of δ¹⁸O values in the δ_{vein quartz}–δ_{host quartzite} space. Calculations show that the likely life span of the post-caldera, hydrothermal activity in the depth range of 2.1–2.3 km beneath Long Valley was 0.08–0.12 Ma. Diffusive ±advective transport of oxygen isotopes from fracture-channelized meteoric water to nearly impermeable wall rocks caused a lowering of δ¹⁸O values in the quartz over short distances and in calcites over greater distances. Thus, the hydrothermal activity appears pervasive even though the meteoric water flow was primarily controlled by fractures.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

Mantle-derived volatiles in continental crust: the Massif Central of France

CO₂-rich gases and groundwaters from springs and boreholes originating within the basement of the Massif Central have variable³He/⁴He ratios with correspondingR/R_a values ranging from 0.8 to 5.5 and 0.3 to 2.8 respectively, indicating the presence of a significant component of mantle helium. Molar concentrations of rare gases in the CO₂-rich gases are approximately 5 orders of magnitude greater than in the waters and suggest that a near-surface Henry's Law fractionation has occurred between exsolving CO₂ and water.δ¹³C values of the CO₂-rich gases are in the range −4.2 to −6.1‰, i.e. in that range normally attributed to mantle carbon, but which could also represent an average crustal composition and therefore do not discriminate between mantle and crustal sources.C/³He ratios show 4 orders of magnitude variation from 1.4 × 10¹² to 5 × 10⁸ and, compared to a mantleC/³He ratio of 10⁹, indicate that either a complex fractionation has occurred between mantle helium and mantle CO₂ or more likely that mantle rare gases have been diluted by large quantities of CO₂ with an average crustal carbon isotope composition. The regional distribution of³He and C does not show any obvious relationship to age or proximity of volcanic centres or major faults, suggesting that mantle-derived C and He components decoupled from their silicate melt sources at some depth.The results from this area of active fluid circulation suggest that C-isotope data derived from metamorphic terrains should be interpreted with great caution, but that input of some mantle-derived carbon is expected to accompany crustal extension.     

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6–2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6‰ in¹⁸O during differentiation is explained by crystallization of¹⁸O-depleted mafic phases. Silicic glasses have elevated δ¹⁸O values and relatively low δD values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary δD values of −53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere.