Geochemical and isotopic evidence for seawater contamination of the hydrothermal system of Taal Volcano, Luzon, the Philippines

 The hydrologic structure of Taal Volcano has favored development of an extensive hydrothermal system whose prominent feature is the acidic Main Crater Lake (pH<3) lying in the center of an active vent complex, which is surrounded by a slightly alkaline caldera lake (Lake Taal). This peculiar situation makes Taal prone to frequent, and sometimes catastrophic, hydrovolcanic eruptions. Fumaroles, hot springs, and lake waters were sampled in 1991, 1992, and 1995 in order to develop a geochemical model for the hydrothermal system. The low-temperature fumarole compositions indicate strong interaction of magmatic vapors with the hydrothermal system under relatively oxidizing conditions. The thermal waters consist of highly, moderately, and weakly mineralized solutions, but none of them corresponds to either water–rock equilibrium or rock dissolution. The concentrated discharges have high Na contents (>3500 mg/kg) and low SO₄/Cl ratios (<0.3). The Br/Cl ratio of most samples suggests incorporation of seawater into the hydrothermal system. Water and dissolved sulfate isotopic compositions reveal that the Main Crater Lake and spring discharges are derived from a deep parent fluid (T≈300  °C), which is a mixture of seawater, volcanic water, and Lake Taal water. The volcanic end member is probably produced in the magmatic-hydrothermal environment during absorption of high-temperature gases into groundwater. Boiling and mixing of the parent water give rise to the range of chemical and isotopic characteristics observed in the thermal discharges. Incursion of seawater from the coastal region to the central part of the volcano is supported by the low water levels of the lakes and by the fact that Lake Taal was directly connected to the China sea until the sixteenth century. The depth to the seawater-meteoric water interface is calculated to be 80 and 160 m for the Main Crater Lake and Lake Taal, respectively. Additional data are required to infer the hydrologic structure of Taal. Geochemical surveillance of the Main Crater Lake using the SO₄/Cl, Na/K, or Mg/Cl ratio cannot be applied straightforwardly due to the presence of seawater in the hydrothermal system. Received: 12 February 1997 / Accepted: 26 January 1998     

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.     

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 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.     

不同水文情景下洪泽湖二氧化碳排放通量特征及影响因素

内陆水域二氧化碳(CO₂)排放是全球碳平衡的重要组成部分,全球CO₂排放通量估算通常有很大不确定性,一方面源于CO₂排放数据观测的时空离散性,另一方面也是缺少水文情景与CO₂排放通量关联性的研究.本文观测了2018年洪泽湖不同水文情景表层水体CO₂排放通量特征,并探讨其影响因素.结果表明,洪泽湖CO₂排放通量为丰水期((106.9±73.4) mmol/(m²·d))>枯水期((18.7±13.6) mmol/(m²·d))>平水期((5.2±15.5) mmol/(m²·d)),且碳通量由丰(310.2~32.0 mmol/(m²·d))、枯(50.8~2.2 mmol/(m²·d))、平(-17.3~39.8 mmol/(m²·d))3种水文情景的交替表现出湖泊碳源到弱碳汇的转变,空间上CO₂排放通量总体呈现北部成子湖区低、南部过水湖区高的分布趋势.洪泽湖CO₂排放对水文情景响应敏感,特别是上游淮河流域来水量的改变,是主导该湖CO₂排放时空分异的重要因子.丰水期湖泊接纳了淮河更多有机和无机碳的输入,外源碳基质的降解和矿化显著促进了水体CO₂的生产与排放,同时氮、磷等营养物质的大量输入,加剧了水体营养化程度,进一步提高CO₂排放量,间接反映出人类活动对洪泽湖CO₂变化的深刻影响.平、枯水期随着上游淮河来水量的减少,驱动水体CO₂排放的因素逐渐由外源输入转变为水体有机质的呼吸降解.此外,上游河口区DOM中陆源类腐殖质的累积与矿化能够促进CO₂的排放,而内源有机质组分似乎并没有直接参与CO₂的排放过程.研究结果揭示了水文情景交替对湖库CO₂排放的重要影响,同时有必要进行高频观测以进一步明晰湖泊的碳通量变化及其控制因素.     

Geochemistry of the Albano and Nemi crater lakes in the volcanic district of Alban Hills (Rome,Italy)

Lake Albano, located 20 km to the SE of Rome, is hosted within the most recent crater of the quiescent Alban Hills volcanic complex that produced hydromagmatic eruptions in Holocene times. Stratigraphic, archaeological and historical evidence indicates that the lake level underwent important variations in the Bronze Age. Before the IV century B.C. several lahars were generated by water overflows from the lake and in the IV century B.C. Romans excavated a drainage tunnel. The lake is located above a buried carbonate horst that contains a pressurized medium-enthalpy geothermal reservoir from which fluids escape to the surface to produce many important gas manifestations of mostly CO₂. Previous studies recognized the presence of gas emissions also from the crater bottom. In 1997 the possibility of a Nyos-type event triggered by a lake rollover was considered very low, because the CO₂ water concentration at depth was found to be far from saturation. However, considering the high population density nearby, the Italian Civil Protection Department recommended that periodical monitoring be carried out. To this scope we initiated in 2001 a systematic geochemical study of the lake. Thirteen vertical profiles have been repeatedly carried out in 2001–2006, especially in the deepest part of the lake (167 m in 2006), measuring T, pH, dissolved O₂ and electrical conductivity. Water samples were collected from various depths and chemically and isotopically analysed. Two similar profiles have been measured also in the nearby Nemi crater lake. Results indicate that in the 4.5 years of monitoring the pressure of gas dissolved in the Lake Albano deep waters remained much lower than the hydrostatic pressure. A CO₂ soil survey carried out on the borders of the two lakes, indicates the presence of some zones of anomalous degassing of likely magmatic origin. A water overturn or a heavy mixing of deep and shallow waters likely occurred in winter 2003–2004, when cold rainfall cooled the surface water below 8.5 °C. Such overturns cause only a limited gas exsolution from the lake when the deep water is brought to a few meters depth but can explain the observed decrease with time of dissolved CO₂ at depth and related water pH increase. A gas hazard could occur in the case of a sudden injection through the lake bottom of a huge quantity of CO₂-rich fluids, which might be caused by earthquake induced fracturing of the rock pile beneath the lake. A limnic gas eruption might also occur should CO₂ concentration build up within the lake for a long time.     

Recent pH and CO2 profiles at Lakes Nyos and Monoun, Cameroon: implications for the degassing strategy and its numerical simulation

In situ pH profiles are reported for the first time for Lakes Nyos and Monoun. The pH profiles were converted to CO₂ profiles using HCO₃⁻ profiles calculated from conductivity data. Recent observations (1993–1996) at Lake Nyos indicates that CO₂ still accumulates below 180 m depth at a rate of 125 Mmol year⁻¹. At Lake Monoun, the majority of CO₂ is present below a depth of 60 m, only 25 m below the saturation depth. Consequently, a potential danger of gas explosion is high at both lakes, and artificial degassing of the lakes should be performed as soon as possible. A system for industrial degassing of the lakes is proposed. The system, based on the self-sustained gas lift principle, consists of multiple pipes (14 cm in diameter) with different intake depths; 12 pipes for Lake Nyos (four each at 185, 195 and 205 m) and three pipes for Lake Monoun (at 70, 80 and 90 m). The stepped degassing at different depths is intended to keep the maximum stability of the lakes. The proposed degassing operation was simulated using the code for both lakes. In 5 years, approximately 50% of currently dissolved CO₂ in Lake Nyos and 90% in Lake Monoun will be removed. The expected changes in the thermal and chemical structures of the lakes as degassing proceeds will be most easily monitored with a carefully calibrated CTD equipped with a pH sensor. The simulation indicates that the discharged degassed water will sink to a level of neutral buoyancy, i.e. to a maximum of 70 m at Lake Nyos and 35 m at Lake Monoun. There would be no possibility of triggering a gas explosion by this plunge of discharged water because the water present there would have already been replaced by water at lower CO₂ concentration, during the degassing from shallower pipes.     

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.     

Acoustic noise and temperature monitoring of the Crater Lake of Mount Ruapehu Volcano

Acoustic signals in Ruapehu Crater Lake, which are now being telemetered via a satellite transmission system, show promise as a possible precursor of increased volcanic activity from Ruapehu. The start of a recent period of rapid heating of Crater Lake was preceded by low-frequency (2 Hz) acoustic signals. These accompanied similar frequency seismic signals, but seemed to be produced independently. Audio-frequency (350–3000 Hz) acoustic noise also showed a very clear peak shortly before the lake temperature started to rise.     

Leakage of Active Crater lake brine through the north flank at Rincón de la Vieja volcano, northwest Costa Rica, and implications for crater collapse

The Active Crater at Rincón de la Vieja volcano, Costa Rica, reaches an elevation of 1750 m and contains a warm, hyper-acidic crater lake that probably formed soon after the eruption of the Rio Blanco tephra deposit approximately 3500 years before present. The Active Crater is buttressed by volcanic ridges and older craters on all sides except the north, which dips steeply toward the Caribbean coastal plains. Acidic, above-ambient-temperature streams are found along the Active Crater's north flank at elevations between 800 and 1000 m. A geochemical survey of thermal and non-thermal waters at Rincón de la Vieja was done in 1989 to determine whether hyper-acidic fluids are leaking from the Active Crater through the north flank, affecting the composition of north-flank streams.Results of the water-chemistry survey reveal that three distinct thermal waters are found on the flanks of Rincón de la Vieja volcano: acid chloride–sulfate (ACS), acid sulfate (AS), and neutral chloride (NC) waters. The most extreme ACS water was collected from the crater lake that fills the Active Crater. Chemical analyses of the lake water reveal a hyper-acidic (pH0) chloride–sulfate brine with elevated concentrations of calcium, magnesium, aluminum, iron, manganese, copper, zinc, fluorine, and boron. The composition of the brine reflects the combined effects of magmatic degassing from a shallow magma body beneath the Active Crater, dissolution of andesitic volcanic rock, and evaporative concentration of dissolved constituents at above-ambient temperatures. Similar cation and anion enrichments are found in the above-ambient-temperature streams draining the north flank of the Active Crater. The pH of north-flank thermal waters range from 3.6 to 4.1 and chloride:sulfate ratios (1.2–1.4) that are a factor of two greater than that of the lake brine (0.60). The waters have an ACS composition that is quite different from the AS and NC thermal waters that occur along the southern flank of Rincón de la Vieja.The distribution of thermal water types at Rincón de la Vieja strongly indicates that formation of the north-flank ACS waters is not due to mixing of shallow, steam-heated AS water with deep-seated NC water. More likely, hyper-acidic brines formed in the Active Crater area are migrating through permeable zones in the volcanic strata that make up the Active Crater's north flank. Dissolution and shallow subsurface alteration of north-flank volcanoclastic material by interaction with acidic lake brine, particularly in the more permeable tephra units, could weaken the already oversteepened north flank of the Active Crater. Sector collapse of the Active Crater, with or without a volcanic eruption, represents a potential threat to human lives, property, and ecosystems at Rincón de la Vieja volcano.     

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     

Time-dependent CO<Subscript>2</Subscript> variations in Lake Albano associated with seismic activity

Lake Albano (Alban Hills volcanic complex, Central Italy) is located in a densely populated area near Rome. The deep lake waters have significant dissolved CO₂ concentrations, probably related to sub-lacustrine fluid discharges fed by a pressurized CO₂-rich reservoir. The analytical results of geochemical surveys carried out in 1989–2010 highlight the episodes of CO₂ removal from the lake. The total mass of dissolved CO₂ decreased from ∼5.8 × 10⁷ kg in 1989 to ∼0.5 × 10⁷ kg in 2010, following an exponential decreasing trend. Calculated values of both dissolved inorganic carbon and CO₂ concentrations along the vertical profile of the lake indicate that this decrease is caused by CO₂ release from the epilimnion, at depth <9 m, combined with (1) water circulation at depth <95 m and (2) CO₂ diffusion from the deeper lake layers. According to this model, Lake Albano was affected by a large CO₂ input that coincided with the last important seismic swarm at Alban Hills in 1989, suggesting an intimate relationship between the addition of deep-originated CO₂ to the lake and seismic activity. In the case of a CO₂ degassing event of an order of magnitude larger than the one that occurred in 1989, the deepest part of Lake Albano would become CO₂-saturated, resulting in conditions compatible with the occurrence of a gas outburst. These results reinforce the idea that a sudden CO₂ input into the lake may cause the release of a dense gas cloud, presently representing the major volcanic threat for this densely populated area.     

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.     

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

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

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.     

Remote and in situ plume measurements of acid gas release from La Soufrière volcano, Guadeloupe

This paper presents the first remote measurements of La Soufrière gas emissions since the fumarolic and seismic reactivation in 1992. The chemical composition of the plumes has been measured from May 2003 to September 2004 using an Open Path Fourier Transform InfraRed (OP-FTIR) spectrometer, up to 15 m downwind the South Crater. HCl is clearly detected (concentration between 2.4 and 12 ppmv) whereas SO₂ and H₂S generally remain below the detection limit of the OP-FTIR. Direct measurements of SO₂ and H₂S near the South Crater with a Lancom III analyzer show a fast decrease of their concentrations with the distance. Calculated Cl / S mass ratios are high: from 9.4 ± 1.7 at 15 m from the vent to 2.8 ± 0.6 at 140 m. The enrichment in HCl of the gas emitted at La Soufrière, observed since 1998, corresponds to the degassing of a magma enriched in Cl and depleted in S. This result agrees with isotopic measurements which suggest a magmatic origin of the gases. Readjustments inside the volcanic system may have taken place during the seismic activity beginning in 1992 and enhance the transfer of magmatic gases to the summit.     

Temperature observations of Crater Lake,Mt Ruapehu,New Zealand,using Temperature Telemetry Bouys

The temperature of the Crater Lake of the active volcano Ruapelm has been recorded by Temperature Telemetry Buoys, to determine if lake temperature is correlated with volcanic activity. These buoys had to be specially designed to cope with the unfavourable environment of Crater Lake. A buoy contains a thermistor to measure the lake temperature, and a radio transmitter to transmit a short signal every few minutes, the interval between signals being a function of temperature. The temperature records obtained from these buoys show that the temperature near the lake surface can vary considerably within a few hours. Some of these variations appear to be caused by disturbances in convective heat transfer occurring in the lake. The occurrence of these short term temperature variations means that there is no simple relation between Crater Lake temperatures and the volcanic activity of Ruapehu. Some rapid increases in temperature followed volcanic earthquakes, but one of the biggest increases in temperature occurred just before a group of earthquakes upder the lake.     

Earthquake swarms to the west of Mt Ruapehu preceding its 1995 eruption

Some months prior to the 1995 eruption of Mt Ruapehu (New Zealand), a series of shallow earthquake swarms occurred about 15–20 km west of the summit of Ruapehu. Several earthquakes in these swarms were felt, and the largest event was M_L 4.8. Crustal earthquakes of M_L≥3.0 within 20 km of the summit of Ruapehu have been rather uncommon in recent years. Furthermore, the two periods of strongest activity were both just before times when the temperature of Crater Lake showed rapid increases. The second of these rapid heating phases was immediately followed by increases in the Mg²⁺ ion concentration in Crater Lake, indicating that chemical interactions were occurring between fresh magmatic material and the lake water. The coincidence between seismicity and lake changes suggested a link with the following eruption. A 1-D simultaneous inversion to locate the earthquakes more accurately showed that most of the earthquakes fell into three spatial clusters, each cluster having a small horizontal cross-section. The predominant depth was about 10–16 km. The b-value of this swarm was 0.74, quite compatible with ordinary tectonic earthquakes. Each cluster of earthquakes lies close to the normal Raurimu Fault which runs predominantly north–south to the west of Ruapehu, with an east-trending branch splaying off near its northern end (see Fig. 1b). Composite focal mechanisms of events in the two more southern clusters are oblique-normal, while the other cluster to the north has an oblique-reverse mechanism. The two oblique-normal mechanisms suggest that extension has occurred on part of the fault. This stress pattern was also observed in the focal mechanism solutions of events that occurred after the eruption, when a denser network of portable seismographs covered the region. Although we cannot definitely connect the occurrence of these swarms to the eruptions later in 1995, there is a strong suggestion that the seismicity was connected to the process of magma movement, which temperature and chemical changes in Crater Lake suggest was occurring during the first half of 1995.     

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.