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.     

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

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

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.     

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.     

Helium isotopes in some historical lavas from Mount Vesuvius

³He/⁴He ratios in lavas erupted during the last 360 years at Mt. Vesuvius are between 2.2 and 2.7 R_A (R_A = atmospheric ratio of 1.39 × 10⁻⁶), and are among the lowest values measured in young volcanic rocks. They are also identical to values measured in summit crater fumaroles sampled during 1987–1991. This agreement indicates that the ³He/⁴He ratio in the crater fumaroles faithfully tracks the magmatic value. The relatively low and uniform ³He/⁴He ratio in the lavas reflects either a mantle source enriched in (U + Th)/³He, or a mixture of magmatic and crustal components.     

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.     

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.     

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

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

Estimating thermal inflow to El Chichón crater lake using the energy-budget,chemical and isotope balance approaches

El Chichón crater lake appeared immediately after the 1982 catastrophic eruption in a newly formed, 1-km wide, explosive crater. During the first 2 years after the eruption the lake transformed from hot and ultra-acidic caused by dissolution of magmatic gases, to a warm and less acidic lake due to a rapid “magmatic-to-hydrothermal transition” — input of hydrothermal fluids and oxidation of H₂S to sulfate. Chemical composition of the lake water and other thermal fluids discharging in the crater, stable isotope composition (δD and δ¹⁸O) of lake water, gas condensates and thermal waters collected in 1995–2006 were used for the mass-balance calculations (Cl, SO₄ and isotopic composition) of the thermal flux from the crater floor. The calculated fluxes of thermal fluid by different mass-balance approaches become of the same order of magnitude as those derived from the energy-budget model if values of 1.9 and 2 mmol/mol are taken for the catchment coefficient and the average H₂S concentration in the hydrothermal vapors, respectively. The total heat power from the crater is estimated to be between 35 and 60 MW and the CO₂ flux is not higher than 150 t/day or ~ 200 gm^− 2 day^− 1.     

Geochemistry of volcanic and hydrothermal gases of Mutnovsky volcano,Kamchatka: evidence for mantle,slab and atmosphere contributions to fluids of a typical arc volcano

We report chemical compositions (major and trace components including light hydrocarbons), hydrogen, oxygen, helium and nitrogen isotope ratios of volcanic and geothermal fluids of Mutnovsky volcano, Kamchatka. Several aspects of the geochemistry of fluids are discussed: chemical equilibria, mixing of fluids from different sources, evaluation of the parent magmatic gas composition and contributions to magmatic vapors of fluids from different reservoirs of the Kamchatkan subduction zone. Among reactive species, hydrogen and carbon monoxide in volcanic vapors are chemically equilibrated at temperatures >300°C with the SO₂-H₂S redox-pair. A metastable equilibrium between saturated and unsaturated light hydrocarbons is attained at close to discharge temperatures. Methane is disequilibrated. Three different sources of fluids from three fumarolic fields in the Mutnovsky craters can be distinguished: (1) magmatic gas from a large convecting magma body discharging through Active Funnel, a young crater with the hottest fumaroles (up to 620°C) contributing ~80% to the total volcanic gas output; (2) volcanic fluid from a separate shallow magma body beneath the Bottom Field of the main crater (96–280°C fumaroles); and (3) hydrothermal fluid with a high relative and absolute concentrations of CH₄ from the Upper Field in the main crater (96–285°C fumaroles). The composition of the parent magmatic gas is estimated using water isotopes and correlations between He and other components in the Active Funnel gases. The He-Ar-N₂ systematics of volcanic and hydrothermal fluids of Mutnovsky are consistent with a large slab-derived sedimentary nitrogen input for the nitrogen inventory, and we calculate that only ~1% of the magmatic N₂ has a mantle origin and <<1% is derived from the arc crust.     

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.     

Hazard map of El Chichón volcano,Chiapas, México: Constraints posed by eruptive history and computer simulations

El Chichón volcano consists of a 2-km wide Somma crater compound cone 0.2 Ma old with peripheral domes with a central crater reactivated several times during the Holocene. The most recent eruption at El Chichón occurred from March 28 to April 4, 1982, resulting in the worst volcanic disaster during historical times in Mexico, killing more than 2000 people and destroying nine towns and small communities. The volcanic hazard map of El Chichón is based on detailed field work that documented twelve eruptions during the last 8000 years, and computer simulations. To validate the results, computer simulations were first performed over pre-1982 topography mimicking the extent of the actual deposits produced and afterwards run over post-1982 topography. These eruptions have produced pyroclastic fall, surge, flow and lahar deposits. Pyroclastic flows have different volumes and Heim coefficients varying from 0.2 (pumice flows), to 0.15 (block-and-ash flows) and 0.10 (ash flows). Simulations using FLOW3D and TITAN2D indicate that pumice flows and block-and-ash flows can fill the moat area and follow main ravines up to distances of ca. 3 km from the crater, with no effect on populations around the volcano. On the other hand, more mobile ash flows related to column-collapse events can reach up to 4 km from the vent, but will always follow the same paths and still not affect surrounding populations. The energy-cone model was used to simulate the outflow of pyroclastic surges based on the 1982 event (H/L = 0.1 and 0.2), and shows that surges may reach some towns around the volcano.     

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.     

Geochemistry of the volcano-hydrothermal system of El Chichón Volcano, Chiapas, Mexico

 The 1982 eruption of El Chichón volcano ejected more than 1 km³ of anhydrite-bearing trachyandesite pyroclastic material to form a new 1-km-wide and 300-m-deep crater and uncovered the upper 500 m of an active volcano-hydrothermal system. Instead of the weak boiling-point temperature fumaroles of the former lava dome, a vigorously boiling crater spring now discharges  / 20 kg/s of Cl-rich (∼15 000 mg/kg) and sulphur-poor ( / 200 mg/kg of SO₄), almost neutral (pH up to 6.7) water with an isotopic composition close to that of subduction-type magmatic water (δD=–15‰, δ¹⁸O=+6.5‰). This spring, as well as numerous Cl-free boiling springs discharging a mixture of meteoric water with fumarolic condensates, feed the crater lake, which, compared with values in 1983, is now much more diluted (∼3000 mg/kg of Cl vs 24 030 mg/kg), less acidic (pH=2.6 vs 0.56) and contains much lower amounts of S ( / 200 mg/kg of SO₄, vs 3550 mg/kg) with δ³⁴S=0.5–4.2‰ (+17‰ in 1983). Agua Caliente thermal waters, on the southeast slope of the volcano, have an outflow rate of approximately 100 kg/s of 71  °C Na–Ca–Cl water and are five times more concentrated than before the eruption (B. R. Molina, unpublished data). Relative N₂, Ar and He gas concentrations suggest extensional tectonics for the El Chichón volcanic centre. The ³He/⁴He and ⁴He/²⁰Ne ratios in gases from the crater fumaroles (7.3R_a, 2560) and Agua Caliente hot springs (5.3R_a, 44) indicate a strong magmatic contribution. However, relative concentrations of reactive species are typical of equilibrium in a two-phase boiling aquifer. Sulphur and C isotopic data indicate highly reducing conditions within the system, probably associated with the presence of buried vegetation resulting from the 1982 eruption. All Cl-rich waters at El Chichón have a common source. This water has the appearence of a "partially matured" magmatic fluid: condensed magmatic vapour neutralized by interaction with fresh volcaniclastic deposits and depleted in S due to anhydrite precipitation. Shallow ground waters emerging around the volcano from the thick cover of fresh pumice deposits (Red waters) are Ca–SO₄–rich and have a negative oxygen isotopic shift, probably due to ongoing formation of clay at low temperatures. Received: 21 July 1997 / Accepted: 4 December 1997     

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).     

Evolution of fumarolic gases — boundary conditions set by measured parameters: case study at Vulcano,Italy

Physical, chemical and isotopic parameters were measured in fumaroles at the Vulcano crater and in drowned fumaroles near the beach. The data were used to define boundary conditions for possible conceptual models of the system.Crater fumaroles: time variations of CO₂ and SO₂ concentrations indicate mixing of saline gas-rich water with local fresh water. Cl/Br ratios of 300– 400 favour sea-water as a major source for Cl, Brand part of the water in the fumaroles. Cl concentrations and D values revealed, independently, amixing of 0.75 sea-water with 0.25 local freshwaterin furmarole F-5 during September 1982.Patterns of parameter correlation and mass balances reveal that CO₂, S, NH₃ and B originate from sources other than sea water. The CO₂ value of ¹³C = – 2%_o favours, at least partial, origin from decomposition of sedimentary rocks rather than mantle-derived material. Radiogenic⁴He(1.3 × lO^–3 ccSTP/g water) and radiogenic⁴⁰Ar(10.6 × 10^–4 ccSTP/g water) are observed, (⁴He/⁴⁰Ar)_radiogenic = 1.2, well in the range of values observed in geothermal systems.Drowned fumaroles: strongly bubbling gas at a pond and at the beachappears to have the same origin and initial compositionas the crater fumaroles (2 km away). The fumarolic gas is modified by depletion of the reactive gases, caused by dissolution in shallow-water. Atmospheric Ne, Ar, Kr and Xe are addeden route, some radiogenic He and Ar are maintained. The Vulcano system seems to be strongly influenced by the contribution of sea-water and decomposition of sedimentary rocks. Evidence of magmatic contributions is mainly derived from heat.     

Sources of chloride in hydrothermal fluids from the Valles caldera, New Mexico: a Cl study

The Valles caldera in New Mexico hosts a high-temperature geothermal system, which is manifested in a number of hot springs discharging in and around the caldera. In order to determine the fluid pathways and the origin of chloride in this system, we measured ³⁶Cl/Cl ratios in waters from high-temperature drill holes and from surface springs in this region. The waters fall into two general categories: recent meteoric water samples with low Cl⁻ concentrations (< 10 mg/L) and relatively high ³⁶Cl/Cl ratios [(300–1000) × 10⁻¹⁵]; and geothermal brines with high Cl⁻ concentrations (800–9400 mg/L) but low ³⁶Cl/Cl ratios [(11–26) × 10⁻¹⁵]. The ³⁶Cl/Cl ratios for meteoric waters are slightly higher than expected for this region, suggesting a small addition of anthropogenic ³⁶Cl. Because of low ³⁶Cl/Cl ratios and high Cl⁻ concentrations in the brines, chloride in these waters must be derived from subsurface sources. A comparison between the observed ³⁶Cl/Cl ratios in the brines and those calculated for potential source formations in this region indicates that the present host formations, mainly volcanic tuffs, cannot be major sources of chloride, and that formations at greater depth, such as the Paleozoic and Precambrian formations are more likely to be sources of chloride in the brines. The results suggest that brines are meteoric waters which penetrated into the basement where they derive chloride from leaching of basement rocks and/or from saline pore fluids trapped there, along with likely addition of chloride from Paleozoic strata. Although these fluids have since come to reside in the intracaldera volcanic sequence after convective upwelling, they do not derive much Cl⁻ from the volcanic strata; and residence times of fluids in the volcanics are < 100,000 years.     

Deep sea explosive activity on the Mid-Atlantic Ridge near 34°50′N: Magma composition, vesicularity and volatile content

Submersible observations and sampling were carried out in the rift valley of the Mid-Atlantic Ridge (MAR) near 34°40′N–35°N. The 4-km-wide rift valley consists of a Neo Volcanic Zone (NVZ) (<1 km wide) bounded at the west by a Median Ridge (MR) (5 km wide and 20 km long) and at the east by the first scarps of the eastern wall. The MR and the eastern wall are characterized by volcanic cones about 200–300 m height culminating at depths of 1500–1900 m which are made up of volcaniclastic deposits (pyroclasts and hyaloclasts) suggestive of explosive volcanism. Based on their surface morphology, degree of vesicularity, and composition, the erupted deposits are classified into four groups: (1) poorly vesicular (<15% vesicles) N- and T-MORBs (K/Ti <0.25, Na₂O+K₂O<2.9%) consisting of sheet flows and pillows formed during fissure eruptions in the NVZ at 2000–2300 m depths; (2) vesicular (15–30% vesicles) E-MORBs (K/Ti=0.25−0.45,Na₂O+K₂O>2.8−3.2%) and alkali basalts (K/Ti=0.45−0.70,Na₂O+K₂O>3.3−4) made up mainly of pillows; (3) highly vesicular (>35% vesicles) pillow lava and pyroclastic (scoria-like) alkali basalts (K/Ti>0.45−0.80,Na₂O+K₂O>3−4%); and (4) hyaloclastites consisting of glassy shards of alkali basalt composition. The total water and carbon contents of the deposits increase with the incompatible element concentrations. The estimated initial H₂O content for the N- and T-MORBs is less than 3500 ppm, whereas for the E-MORBs and alkali basalts the H₂O content is near 4000 and 7000 ppm, respectively. While the H₂O is mainly in the melt, the carbon is in the form of CO₂ filling vesicles. The vesicles are formed from magma with an initial carbon content of 1000–3000 for the N- and T-MORBs, 3000–6500 ppm for the E-MORBs and higher than 1 wt% for the alkali basalts.The various lava types were derived from a heterogeneous mantle source composed of enriched and depleted components during sequential eruptions of N-, T- and E-MORBs and alkali basalts (K/Ti>0.7). The amount of CO₂ and H₂O in equilibrium with the dissolved species present in the vesicles indicates that CO₂ (XCO₂=1−0.84) was the main exsolved compound responsible for bubble nucleation. The increase in the degree of vesicularity and pressure of the volatile phases is mainly due to the early exsolution of CO₂ from an alkali melt. The exsolution of significant amounts of dissolved water occurred only for the alkali basalt a few hundred meters beneath the seafloor and contributed to late bubble expansion. This subsequent addition of magmatic water to the vesicles increased the gas pressure and triggered explosions. An alternative hypothesis for the explosive volcanism is based on field observations. During crater collapsed, seawater could have been trapped in fractured volcanic conduits and later sealed by hydrothermal fluid circulation and precipitation. In such an environment, this seawater will be heated and vaporized during renewed magmatic upwelling. Both scenarios give rise to fragmented debris (hyaloclasts and pyroclasts) and the explosive events create turbulent flows followed by differential gravity settling of the particles (shards versus lapilli) through the seawater.     

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

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

The ClBrI composition of 3.23 Ga modified seawater: implications for the geological evolution of ocean halide chemistry

Fluid inclusion leachates obtained from vug and vein quartz samples from an Archean (3.23 Ga) Fe-oxide hydrothermal deposit in the west-central part of the Barberton greenstone belt, South Africa, were analyzed by ion chromatography for chloride, bromide, and iodide. The deposit, known as the ironstone pods, formed by seafloor hydrothermal activity and fluid discharge. Quartz is dominated by type I liquid-vapor, aqueous inclusions with a bimodal salinity distribution (0–0.25 M_Cl⁻ and 0.9–1.8 M_Cl⁻). Bulk analytical salinities range from 0.45 to 0.99 M_Cl⁻ represent averages of type I inclusions. Bulk fluid inclusion bromide and iodide concentrations are 1.44–3.32 mM and 0.01–0.12 mM, respectively. For comparison, modern seawater has halogen contents of 590 mM chloride, 0.9 mM bromide, and 0.5 μM total iodine. In the fluids from the ironstone pods, bromide and iodide are enriched relative to chloride, when compared with modern seawater.Approximate Br⁻Cl⁻ and I⁻Cl⁻ ratios of 3.2 Ga Barberton seawater are 2.5 × 10⁻³ and 40 × 10⁻⁶, respectively. Dispersion to higher values was caused principally by reaction with organic sediments whose trends are similar to those seen for modern vent fluids at unsedimented and sedimented ridges, relative to modern seawater. These halide ratios are greater than those of modern seawater, suggesting a change in the halide ratios of seawater over geological time. The analytical data are consistent with a model in which marine organic sedimentation has fractionated bromine and iodine out of seawater relative to chloride, thereby causing the halide ratios of seawater to decrease from high early and mid-Archean values towards their present day values.