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.     

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.     

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.     

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

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

Chemical evolution and volcanic activity of the active crater lake of Poás volcano, Costa Rica, 1993–1997

Concentrations of chloride and sulfate and pH in the hot crater lake (Laguna Caliente) at Poás volcano and in acid rain varied over the period 1993–1997. These parameters are related to changes in lake volume and temperature, and changes in summit seismicity and fumarole activity beneath the active crater. During this period, lake level increased from near zero to its highest level since 1953, lake temperature declined from a maximum value of 70°C to a minimum value of 25°C, and pH of the lake water increased from near zero to 1.8. In May 1993 when the lake was nearly dry, chloride and sulfate concentrations in the lake water reached 85,400 and 91,000 mg l⁻¹, respectively. Minimum concentrations of chloride and sulfate after the lake refilled to its maximum volume were 2630 and 4060 mg l⁻¹, respectively. Between January 1993 and May 1995, most fumarolic activity was focused through the bottom of the lake. After May 1995, fumarolic discharge through the bottom of the lake declined and reappeared outside the lake within the main crater area. The appearance of new fumaroles on the composite pyroclastic cone coincided with a dramatic decrease in type B seismicity after January 1996. Between May 1995 and December 1997, enhanced periods of type A seismicity and episodes of harmonic tremor were associated with an increase in the number of fumaroles and the intensity of degassing on the composite pyroclastic cone adjacent to the crater lake. Increases in summit seismic activity (type A, B and harmonic tremor) and in the height of eruption plumes through the lake bottom are associated with a period of enhanced volcanic activity during April–September 1994. At this time, visual observations and remote fumarole temperature measurements suggest an increase in the flux of heat and gases discharged through the bottom of the crater lake, possibly related to renewed magma ascent beneath the active crater. A similar period of enhanced seismic activity that occurred between August 1995 and January 1996, apparently caused fracturing of sealed fumarole conduits beneath the composite pyroclastic cone allowing the focus of fumarolic degassing to migrate from beneath the lake back to the 1953–1955 cone. Changes in the chemistry of summit acid rain are correlated changes in volcanic activity regardless of whether fumaroles are discharging into the lake or are discharging directly into the atmosphere.     

Major and trace element geochemistry of neutral and acidic thermal springs at El Chichón volcano,Mexico: Implications for monitoring of the volcanic activity

Four groups of thermal springs with temperatures from 50 to 80 °C are located on the S–SW–W slopes of El Chichón volcano, a composite dome-tephra edifice, which exploded in 1982 with a 1 km wide, 160 m deep crater left. Very dynamic thermal activity inside the crater (variations in chemistry and migration of pools and fumaroles, drastic changes in the crater lake volume and chemistry) contrasts with the stable behavior of the flank hot springs during the time of observations (1974–2005). All known groups of hot springs are located on the contact of the basement and volcanic edifice, and only on the W–SW–S slopes of the volcano at almost same elevations 600–650 m asl and less than 3 km of direct distance from the crater. Three groups of near-neutral (pH ≈ 6) springs at SW–S slopes have the total thermal water outflow rate higher than 300 l/s and are similar in composition. The fourth and farthest group on the western slope discharges acidic (pH ≈ 2) saline (10 g/kg of Cl) water with a much lower outflow rate (< 10 l/s).     

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.     

A telemetering system for monitoring aqueous polythionates in an active crater lake

We have developed an in-situ monitoring system for aqueous polythionates in the Yugama crater lake at Kusatsu-Shirane volcano. A commercially available nitrate-selective electrode has a Nernstian response to the concentration of polythionates in solution in the range of pH 2.5–11. However, many active crater lakes contain highly acidic water (pH ranges from 0.2 to 2). The monitoring system reduces the acidity of the lake water to pH 4 without changing the concentration of polythionates using a high efficiency cation-exchange membrane technique. The monitoring system was placed in a submersed station, because the Yugama surface lake water freezes in mid-winter. The system is described and preliminary data are reported.     

A water flow model of the active crater lake at Aso volcano,Japan: fluctuations of magmatic gas and groundwater fluxes from the underlying hydrothermal system

The first crater of Nakadake, peak of Aso volcano, Japan, contains a hot water lake that shows interesting variations in water level and temperature. These variations were discovered by precise, continuous observations of the lake independent of precipitation. We developed a numerical model of a hot crater lake and compared with observational data for the period from July 2006 to January 2009. The numerical model revealed seasonal changes in mass flux (75–132 kg/s) and enthalpy (1,840–3,030 kJ/kg) for the fluid supplied to the lake. The relation between the enthalpy and mass flux indicates that the bottom input fluid is a mixture of high- and low-temperature fluids. Assuming a mixture of high-temperature steam at 800°C and liquid water at 100°C, we evaluated the liquid and steam fluxes. The liquid water flux shows a seasonal increase lagging behind the rainy season by 2 months, suggesting that the liquid water is predominantly groundwater. The fluctuation pattern in the flux of the high-temperature steam shows a relation with the amplitude of volcanic tremor, suggesting that heating of the hydrothermal system drives the tremor. Consequently, precise observations of a hot crater lake represent a potential method of monitoring volcanic hydrothermal systems in the shallow parts of the volcanoes.     

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.     

Conservative behavior of arsenic and other oxyanion-forming trace elements in an oxic groundwater flow system

Groundwater samples were collected along a flow path in a shallow, fractured tuffaceous aquifer from the Oasis Valley–Beatty Wash region of southern Nevada, USA, and analyzed for a number of oxyanion-forming trace elements including arsenic (As), antimony (Sb), selenium (Se), molybdenum (Mo), and tungsten (W). In addition, ancillary geochemical parameters, including pH, major solute compositions, dissolved silica, dissolved oxygen, and iron and manganese concentrations were quantified in the groundwaters. Arsenic concentrations range from 70 nmol/kg up to 316 nmol/kg in groundwaters of the Oasis Valley–Beatty Wash flow system, and generally exhibit increasing concentrations with flow down-gradient along the flow path. Antimony, W, and to a lesser extent, Mo, exhibit similar increasing concentration trends with flow down-gradient in the aquifer, albeit, at lower concentrations levels (e.g., mean ± SD for Sb, W, and Mo are 2.3 ± 0.9 nmol/kg, 7.4 ± 3.7 nmol/kg, and 101 ± 19 nmol/kg, respectively). Selenium concentration, which range between 4 and 11 nmol/kg, generally decrease in groundwaters with flow down-gradients in the Oasis Valley–Beatty Wash groundwater flow systems. Inverse modeling of groundwater chemistry evolution from the lower reaches of the Oasis Valley flow path using PHREEQC indicate that the groundwater composition is consistent with mixing of nearly equal proportions of groundwater from upper reaches of Oasis Valley and Beatty Wash groundwater, along with dissolution of volcanic glass, potassium feldspar, and gypsum, followed by calcite precipitation, and formation of secondary zeolites (analcime), clay minerals (Ca-montmorillonite), and cristobalite. The geochemical modeling indicates that the concentrations of As and the other oxyanion-forming trace elements are controlled by dissolution of volcanic glass, water–rock interaction with mineralized zones within the aquifer (i.e., sulfide oxidation), desorption from aquifer surface sites, and mixing of Oasis Valley and Beatty Wash groundwaters.     

A reconnaissance geochemical study of La Primavera geothermal area, Jalisco, Mexico

The Sierra La Primavera, a late Pleistocene rhyolitic caldera complex in Jalisco, México, contains fumaroles and large-discharge 65°C hot springs that are associated with faults related to caldera collapse and to later magma insurgence. The nearly-neutral, sodium bicarbonate, hot springs occur at low elevations at the margins of the complex, whereas the water-rich fumaroles are high and central.The Comisión Federal de Electricidad de México (CFE) has recently drilled two deep holes at the center of the Sierra (PR-1 and Pr-2) and one deep hole at the western margin. Temperatures as high as 285°C were encountered at 1160 m in PR-1, which produced fluids with 820 to 865 mg/kg chloride after flashing to one atmosphere. Nearby, PR-2 encountered temperatures to 307°C at 2000 m and yielded fluids with chloride contents fluctuating between 1100 and 1560 mg/kg after flashing. Neither of the high-temperature wells produced steam in commercial quantities. The well at the western margin of the Sierra produced fluids similar to those from the hot springs. The temperature reached a maximum of 100°C near the surface and decreased to 80°C at 2000 m.Various geothermometers (quartz conductive, Na/K, Na-K-Ca, δ¹⁸O(SO₄-H₂O) and D/H (steam-water) all yield temperatures of 170 ± 20°C when applied to the hot spring waters, suggesting that these spring waters flow from a large shallow reservoir at this temperature. Because the hot springs are much less saline than the fluids recovered in PR-1 and PR-2, the mixed fluid in the shallow reservoir can contain no more than 10–20% deep fluid. This requires that most of the heat is transferred by steam. There is probably a thin vapor-dominated zone in the central part of the Sierra, through which steam and gases are transferred to the overlying shallow reservoir. Fluids from this reservoir cool from 170°C to 65°C by conduction during the 5–7 km of lateral flow to the hot springs.     

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

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

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     

Discovery of a recurrent lava lake on Saunders Island (South Sandwich Islands) using AVHRR imagery

Monitoring of the remote South Sandwich Islands volcanic arc, using advanced very high resolution radiometer (AVHRR) data, has identified a radiant pixel on channels 3 (3.55–3.93 μm) and (rarely) 4 (10.3–11.3 μm). The position of the pixel is coincident with Mount Michael, Saunders Island, the active summit crater of a snow-covered basaltic stratovolcano with a persistent steam plume. The radiant pixel was continuously present in successive AVHRR images acquired during intervals of several months in the period examined (March 1995–February 1998), although apparently disappearing for similar time intervals. More than 5000 images were examined during this study. The radiant pixel is interpreted to indicate that the crater has contained a lava lake, the first to be recorded in the South Sandwich Islands. The lake appears to persist in the crater for several months at a time, at least. It may have drained completely at times and was probably absent when the crater was viewed briefly during an overflight in January 1997. Persistent or recurring lava lakes are very uncommon world-wide and that at Mount Michael is one of only two recorded in the Antarctic region.     

Modeling Groundwater Inflow to the New Crater Lake at Kīlauea Volcano,Hawai'i

During the 2018 eruption of Kīlauea Volcano, Hawai'i, scientists relied heavily on a conceptual model of explosive eruptions triggered when lava-lake levels drop below the water table. Numerical modeling of multiphase groundwater flow and heat transport revealed that, contrary to expectations, liquid water inflow to the drained magma conduit would likely be delayed by months to years, owing to the inability of liquid water to transit a zone of very hot rock. The summit of Kīlauea subsequently experienced an ∼2-month period of consistent repeated collapses, and the crater now extends below the equilibrium position of the water table. Liquid water first emerged into the deepened crater in late July 2019. The timing of first appearance of liquid water (about 14 months postcollapse) and the rate of crater lake filling (currently ∼27 kg/s) were well-predicted by the numerical modeling done in late spring 2018, which forecast liquid inflow after 3 to 24 months at rates of 10 to 100 kg/s. A second-generation groundwater model, reflecting the current crater geometry, forecasts lake filling over the next several years. The successful 2018 to present forecasts with both models are based on unadjusted in situ permeability estimates (1 to 6 × 10⁻¹⁴ m²) and water-table elevations (600 to 800 m) from a nearby research drillhole and geophysical surveys. Important unknowns that affect the reliability of longer-term forecasts include the equilibrium water-table geometry, the rate of evaporation from the hot and growing crater lake (currently ∼29,000 m² at 70-80 °C), and heterogenous permeability changes caused by the 2018 collapse.     

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.     

Guagua pichincha volcano, Ecuador: fluid geochemistry in volcanic surveillance

The densely populated metropolitan area of Quito is located on the slopes of the active Guagua Pichincha volcano at only 10 km from the crater. Recently, the Italian Ministry of Foreign Affairs sponsored a project for the mitigation of volcanic hazard in this area. The geochemical study carried out as part of this project was aimed at constructing a geochemical model of the zone for use in volcanic surveillance.According to this geochemical model, a hydrothermal aquifer (T = 200–240°C), fed both by meteoric waters and by fluids released by a magma body, lies at shallow levels beneath Guagua Pichincha crater. The crater fumaroles are essentially fed by steam boiled off from the hydrothermal aquifer. The high flow rate fumaroles located in the dome area show significant SO₂ contents, which suggest a relatively high contribution of magmatic fluids in the zone of the aquifer feeding them. The absence of SO₂ in the fumarolic discharges near the southern crater wall indicates instead that the magmatic fluids dissolve entirely into the aquifer here. The hot springs located at the western end of the crater represent the lateral discharge of the hydrothermal aquifer.On the basis of this model, it is likely that an increment in the flux of both the magmatic fluids and the heat from a magma body produces an increase, albeit small, of the pressure-temperature conditions of the hydrothermal system and consequent changes in flow rate and fluid chemistry of the fumarolic vents. In particular, total sulphur and possibly hydrochloric acid may increase in all the vents and sulphur dioxide may appear in other fumarolic discharges. The varying thermodynamic conditions in the hydrothermal aquifer can be evaluated on the basis of the equilibria among carbon species and hydrogen. Only minor delayed changes are expected in the physical-chemical characteristics of the springs located at the western end of the crater.     

Hydrogeochemistry of the Simav geothermal field, western Anatolia, Turkey

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

Subsurface formation of oxidants on Mars and implications for the preservation of organic biosignatures

Hydrogen peroxide can form through the interaction of pyrite and anoxic water. The oxidation of pyrite results in the precipitation of sulfates and iron oxides, high redox potentials (~ 1000 mV) and acidic pH (3–4). The oxidative potential of the resultant solution may be responsible for the oxidation of organic compounds, as observed in the subsurface of the Rio Tinto Mars analog. On Mars subsurface migration of groundwater interacting with volcanogenic massive pyrite deposits would have mobilized acidic and oxidizing fluids through large portions of the crust, resulting in the widespread deposition of sulfates and iron oxides. This groundwater could have leached substantial volumes of aquifer material and crustal rocks, thereby erasing any organic compounds possibly down to depths of hundreds of meters. Therefore, the preservation of organic biosignatures must have been severely constrained in the portions of the ancient Martian crust that were exposed to aqueous processes, calling for a redefinition of the future targets in the search for biomolecular traces of life on Mars.