The volcanic acidification of glacial Lake Caviahue,Province of Neuquen,Argentina

Lake Caviahue (northern Patagonia, Argentina) is a large glacial lake acidified by volcanic fluids from Copahue volcano. The lake and the feeding rivers were sampled annually from 1997 till early 2006, including the eruptive period of 2000. Lake Caviahue waters evolved over time, with the most concentrated waters in 2000 during the eruptive period, followed by gradual dilution that was interrupted by renewed acidification in 2003–2004. Inversion of the lake water data and application of a dynamic non-steady state model for the lake provides our best quantitative estimates for the variation in element fluxes over the 9-year period. The model flux results agree well with most of the measured fluxes. The Copahue hydrothermal system had gently declining element fluxes between 1997 and mid-1999, although the lake was still becoming more concentrated. About 2–3 months before the 2000 eruption, element fluxes increased strongly, but the hydrothermal fluxes almost shutoff directly after the main eruptive events. The fluxes of several elements recovered post-2001, with an increase in element fluxes in 2003–2004; the lake became more dilute between 2004 and 2006. The intrusion of new magma into the hydrothermal system just prior to the 2000 eruption led to enhanced water rock interaction, with higher concentrations of the rock forming elements in the fluids, and the hot spring flow rate increased as a result of the higher pressure in the reservoir. The fluids became saturated in alunite and jarosite, and they were already saturated with anhydrite. Precipitation of these minerals possibly led to a decreased permeability of the hydrothermal reservoir, leading to the strongly reduced element fluxes just after the eruption. In addition, K, Al and S were retained in the newly precipitated minerals as well, further diminishing their export. The acidification in 2003–2004 may have resulted from a new small intrusion of magma or resulted from seismic activity that created new permeability and fresh rock surfaces for water rock interaction. The volcano is a significant source of toxic trace elements such as F, As, B and Li as well as a nutrient (P) for the local watershed. Monitoring of the hydrothermal fluids in the river that drains Copahue, especially the S/Cl, Mg/Cl and Mg/K values as well as the magnitude of the element fluxes would provide the best information for eruption forecasting for this volcano.     

Distribution and significance of hydrothermal alteration minerals in the Tuzla hydrothermal system, Çanakkale, Turkey

Hydrothermal alteration zones have been investigated by X-ray diffraction, mineralogical–petrographical techniques, and geochemical analysis. Examination of cores and cuttings from two drill sites, obtained from a depth of about 814–1020 m, show that the hydrothermal minerals occuring in the rock include: K-feldspar, albite, chlorite, alunite, kaolinite, smectite, illite, and opaque minerals.In the studied area, silicified, smectite, illite, alunite, and opal zones have been recognized. These alteration mineral assemblages indicate that there are geothermal fluids, which have temperatures of 150–220°C in the reservoir.The distribution of the hydrothermal minerals shows changes in the chemical composition of the hydrothermal fluid, which are probably due not only to interaction with host rock, but also to dilution of the Na–K–Cl-rich hydrothermal fluid of the deep reservoir by cold sea water at shallow levels. Geochemical analyses of the solid and liquid phases indicate that the hydrothermal fluids of the Tuzla geothermal system are in equilibrium with alteration products.The tectonic structure of the studied area is caused by NW–SE and NE–SW directional forces. The volcanic rocks where hydrothermal zones are observed in the studied area are of Lower–Middle Miocene age comprise latite, andesite, dacite, rhyolite-type lavas, tuff, and ignimbrites.     

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.     

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.     

Volcanic lake systematics I. Physical constraints

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

Water column anomalies associated with hydrothermal activity in the Guaymas Basin,Gulf of California

Sea floor hydrothermal activity in the Guaymas Basin, Gulf of California, is quite different from that associated with ridge crest spreading centers. Injection of hydrothermal fluids occurs in the bottom of a semi-enclosed basin and water column anomalies produced by this activity increase to much higher values than in the open ocean. In the Guaymas Basin the hydrothermal venting generates large clouds of fine suspended particulate matter (SPM) 100–300 m above active mounds and chimneys. These hydrothermal clouds have potential temperature anomalies of about 0.010–0.020°C, are enriched in dissolved silica, particulate manganese, and depleted in dissolved oxygen relative to areas away from the vents. The particulate manganese values increase from about 3 nmol/kg at ～ 1000 m, well above the enclosing topography of the subsill basin, to 100–150 nmol/kg in the clouds of SPM and in the bottom nepheloid layer. The particulate Mn in the hydrothermal clouds appears to originate from both direct precipitation of dissolved Mn²⁺ injected by the vents and entrainment of Mn-rich SPM in the rising hydrothermal plumes. Injection of silica-rich vent fluids into the basin bottom waters produces a silica anomaly of 10–15 μmol relative to the other deep basins of the Gulf of California. Spillover of Guaymas Basin deep water produces a silica plume just above the basin sill depth which is detectable to the mouth of the Gulf. A simple two-endmember mixing model indicates that the deep waters of the Guaymas Basin contain approximately 0.1% hydrothermal fluid. Oxygen anomalies associated with the hydrothermal clouds are on the order of 5 μmol relative to regions away from active vents. The basin as a whole shows a depletion in oxygen of about 13 μmol relative to the other deep basins of the Gulf. The mixing model shows that this oxygen consumption can be explained by the oxidation of dissolved sulfide and methane injected by the hydrothermal vents. Box models of the deep basins of the southern Gulf of California indicate that the Guaymas Basin has a significantly higher source term for dissolved silica and sink term for dissolved oxygen than the other basins. The calculated flux of hydrothermal fluids into the Guaymas Basin is 10–12 m³/s.     

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO₂ concentrations reached 1000 mg/kg in the lower stratum. Loss of CO₂ from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO₄ and HCO₃ contents of Lake Quilotoa are intermediate between those of acid–SO₄–Cl Crater lakes and those of neutral-HCO₃ Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO₄–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO₂ (3×10¹¹ g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO₂-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

Geochemical evidence of hydrothermal recharge in Lake Baringo,central Kenya Rift Valley

Lake Baringo, a freshwater lake in the central Kenya Rift Valley, is fed by perennial and ephemeral rivers, direct rainfall, and hot springs on Ol Kokwe Island near the centre of the lake. The lake has no surface outlet, but despite high evaporation rates it maintains dilute waters by subsurface seepage through permeable sediments and faulted lavas. New geochemical analyses (major ions, trace elements) of the river, lake, and hot spring waters and the suspended sediments have been made to determine the main controls of lake water quality. The results show that evaporative concentration and the binary mixing between two end members (rivers and thermal waters) can explain the hydrochemistry of the lake waters. Two zones are recognized from water composition. The southern part of the lake near sites of perennial river inflow is weakly influenced by evaporation, has low total dissolved species (TDS), and has a seasonally variable load of mainly detrital suspended sediments. In contrast, waters of the northern part of the lake show evidence for strong evaporation (TDS of up to eight times inflow). Authigenic clay minerals and calcite may be precipitating from those more concentrated fluids. The subaerial hot‐spring waters have a distinctive chemistry and are enriched in some elements that are also present in the lake water. Comparison of the chemical composition of the inflowing surface waters and lake water shows (1) an enrichment of some species (HCO₃^?, Cl, SO₄^2?, F, Na, B, V, Cr, As, Mo, Ba and U) in the lake, (2) a depletion in SiO₂ in the lake, and (3) a possible hydrothermal origin for most F. The rare earth element distribution and the F/Cl and Na/Cl ratios give valuable information on the rate of mixing of the river and hydrothermal fluids in the lake water. Calculations imply that thermal fluids may be seeping upward locally into the lake through grid‐faulted lavas, particularly south of Ol Kokwe Island. Copyright © 2006 John Wiley & Sons, Ltd.     

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     

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     

Natural tracers for identifying the origin of the thermal fluids emerging along the Aegean Volcanic arc (Greece): Evidence of Arc-Type Magmatic Water (ATMW) participation

The Aegean volcanic arc is the result of a lithosphere subduction process during the Quaternary time. Starting from the Soussaki area, from west to east, the arc proceeds through the islands of Egina, Methana, Milos, Santorini, the Columbus Bank, Kos and Nisyros. Volcano-tectonic activities are still pronounced at Santorini and Nisyros in form of seismic activity, craters of hydrothermal explosions, hot fumaroles and thermal springs. A significant number of cold water springs emerge in the vicinity of hot waters on these islands.Chemical and isotopic analyses were applied on water and fumaroles samples collected in different areas of the volcanic arc in order to attempt the assessment of these fluids. Stable isotopes of water and carbon have been used to evaluate the origin of cold and thermal water and CO₂.Chemical solute concentrations and isotopic contents of waters show that the fluids emerging in Egina, Soussaki, Methana and Kos areas represent geothermal systems in their waning stage, while the fluids from Milos, Santorini and Nisyros proceed from active geothermal systems.The δ²H–δ¹⁸O–Cl^? relationships suggest that the parent hydrothermal liquids of Nisyros and Milos are produced through mixing of seawater and Arc-Type Magmatic Water (ATMW), with negligible to nil contribution of local ground waters and with very high participation of the magmatic component, which is close to 70% in both sites. A very high magmatic contribution to the deep geothermal system could occur at Santorini as well, perhaps with a percentage similar to Nisyros and Milos, but it cannot be calculated because of steam condensation heavily affecting the fumarolic fluids of Nea Kameni before the surface discharge.The parent hydrothermal liquid at Methana originates through mixing of local groundwaters, seawater and ATMW, with a magmatic participation close to 19%. All in all, the contribution of ATMW is higher in the central–eastern part of the Aegean volcanic arc than in the western sector. This difference, which is spotted in the variable isotopic composition of the sampled fluids from west to east along the arc, is probably due to several causes, including the tectonic regime, the depth of the deep reservoir below sea level, the age of volcanic activity and in general the geomorphologic state of each island.     

Chemical composition of fumarolic gases and spring discharges from El Chichòn volcano, Mexico: causes and implications of the changes detected over the period 1998–2000

Since the March–April 1982 eruption of El Chichòn volcano, intense hydrothermal activity has characterised the 1-km-wide summit crater. This mainly consists of mud and boiling pools, fumaroles, which are mainly located in the northwestern bank of the crater lake. During the period 1998–2000, hot springs and fumaroles discharging inside the crater and from the southeastern outer flank (Agua Caliente) were collected for chemical analyses. The observed chemical fluctuations suggest that the physico-chemical boundary conditions regulating the thermodynamic equilibria of the deep rock/fluid interactions have changed with time. The chemical composition of the lake water, characterised in the period 1983–1997 by high Na⁺, Cl⁻, Ca²⁺ and SO₄²⁻ contents, experienced a dramatic change in 1998–1999, turning from a Na⁺–Cl⁻- to a Ca²⁺–SO₄²⁻-rich composition. In June 2000, a relatively sharp increase in Na⁺ and Cl⁻ contents was observed. At the same time, SO₂/H₂S ratios and H₂ and CO contents in most gas discharges increased with respect to the previous two years of observations, suggesting either a new input of deep-seated fluids or local variations of the more surficial hydrothermal system. Migration of gas manifestations, enhanced number of emission spots and variations in both gas discharge flux and outlet temperatures of the main fluid manifestations were also recorded. The magmatic-hydrothermal system of El Chichòn is probably related to interaction processes between a deep magmatic source and a surficial cold aquifer; an important role may also be played by the interaction of the deep fluids with the volcanic rocks and the sedimentary (limestone and evaporites) basement. The chemical and physical changes recorded in 1998–2000 were possibly due to variations in the permeability of the conduit system feeding the fluid discharges at surface, as testified by the migration of gas and water emanations. Two different scenarios can be put forward for the volcanic evolution of El Chichòn: (1) build-up of an infra-crater dome that may imply a future eruption in terms of tens to hundreds of years; (2) minor phreatic–phreatomagmatic events whose prediction and timing is more difficult to constrain. This suggests that, unlike the diminished volcanic activity at El Chichòn after the 1982 paroxistic event, the volcano-hydrothermal fluid discharges need to be more constantly monitored with regular and more frequent geochemical sampling and, at the same time, a permanent network of seismic stations should be installed.     

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.     

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.     

Seismicity at White Island volcano, New Zealand: a revised classification and inferences about source mechanism

The classification of earthquakes at White Island volcano, New Zealand, has been revised to address problems in existing classification schemes, to better reflect new data and to try to focus more on source processes. Seismicity generated by the direct involvement of magmatic or hydrothermal fluids are referred to as volcanic, and that generated by fault movement in response to stresses caused by those fluids, regional stresses, thermal effects and so on are referred to as volcano-tectonic. Spasmodic bursts form a separate category, as we have insufficient information to classify them as volcanic or volcano-tectonic. Volcanic seismicity is divided into short-duration, long-period volcanic earthquakes, long-duration volcanic earthquakes, and harmonic- and non-harmonic volcanic tremor, while volcano-tectonic seismicity is divided into shallow and deep volcano-tectonic earthquakes. Harmonic volcanic tremor is related to sub-surface intrusive processes, while non-harmonic volcanic tremor originates close to active craters at shallow depth, and usually occurs during eruptive activity. Short-duration, long-period volcanic earthquakes come from a single source close to the active craters, but originate deeper than non-harmonic volcanic tremor, and are not related to eruptive activity. Long-duration volcanic earthquakes often accompany larger discrete eruptions. The waveform of these events consists of an initial low-frequency part from a deep source, and a later cigar-shaped part of mixed frequencies from a shallow crater source.     

Time-space variation of volcano-seismic events at La Fossa (Vulcano, Aeolian Islands, Italy): new insights into seismic sources in a hydrothermal system

We investigated the relationship between volcano-seismic events, recorded at La Fossa crater of Vulcano (Aeolian Islands, Italy) during 2004-2006, and the dynamics of the hydrothermal system. During the period of study, three episodes of increasing numbers of volcano-seismic events took place at the same time as geothermal and geochemical anomalies were observed. These geothermal and geochemical anomalies have been interpreted as resulting from an increasing deep magmatic component of the hydrothermal fluids. Three classes of seismic events (long period, high frequency and monochromatic events), characterised by different spectral content and various similarity of the waveforms, have been recognised. These events, clustered mainly below La Fossa crater area at depths of 0.5–1.1 km b.s.l., were space-distributed according to the classes. Based on their features, we can infer that such events at Vulcano are related to two different source mechanisms: (1) fracturing processes of rocks and (2) resonance of cracks (or conduits) filled with hydrothermal fluid. In the light of these source mechanisms, the increase in the number of events, at the same time as geochemical and geothermal anomalies were observed, was interpreted as the result of an increasing magmatic component of the hydrothermal fluids, implying an increase of their flux. Indeed, such variation caused an increase of both the pore pressure within the rocks of the volcanic system and the amount of ascending fluids. Increased pore pressures gave rise to fracturing processes, while the increased fluid flux favoured resonance and vibration processes in cracks and conduits. Finally, a gradual temporal variation of the waveform of the hybrid events (one of the subclasses of long period events) was observed, likely caused by heating and drying of the hydrothermal system.     

The magmatic- and hydrothermal-dominated fumarolic system at the Active Crater of Lascar volcano,northern Chile

Low-to-high temperature fumaroles discharging from the Active Crater of Lascar volcano (northern Chile) have been collected in November 2002, May 2005 and October 2006 for chemical and isotopic analysis to provide the first geochemical survey on the magmatic-hydrothermal system of this active volcano. Chemical and isotopic gas composition shows direct addition of high-temperature fluids from magmatic degassing, mainly testified by the very high contents of SO₂, HCl and HF (up to 87,800, 29,500 and 2,900 μmol/mol) and the high R/Ra values (up to 7.29). Contributions from a hydrothermal source, mainly in gas discharges of the Active Crater rim, has also been detected. Significant variations in fluid chemistry, mainly consisting of a general decrease of magmatic-related compounds, i.e. SO₂, have affected the fumarolic system during the period of observation, indicating an increase of the influence of the hydrothermal system surrounding the ascending deep fluids. The chemical composition of Active Crater fumaroles has been used to build up a geochemical model describing the main processes that regulate the fluid circulation system of Lascar volcano to be utilized in volcanic surveillance.     

Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys

Many of the heaviest and lightest natural zinc (Zn) isotope ratios have been discovered in hydrothermal ore deposits. However, the processes responsible for fractionating Zn isotopes in hydrothermal systems are poorly understood. In order to better assess the total range of Zn isotopes in hydrothermal systems and to understand the factors which are responsible for this isotopic fractionation, we have measured Zn isotopes in seafloor hydrothermal fluids from numerous vents at 9–10°N and 21°N on the East Pacific Rise (EPR), the TAG hydrothermal field on the Mid-Atlantic Ridge, and in the Guaymas Basin. Fluid δ⁶⁶Zn values measured at these sites range from + 0.00‰ to + 1.04‰. Of the many physical and chemical parameters examined, only temperature was found to correlate with fluid δ⁶⁶Zn values. Lower temperature fluids (< 250 °C) had both heavier and more variable δ⁶⁶Zn values compared to higher temperature fluids from the same hydrothermal fields. We suggest that subsurface cooling of hydrothermal fluids leads to precipitation of isotopically light sphalerite (Zn sulfide), and that this process is a primary cause of Zn isotope variation in hydrothermal fluids. Thermodynamic calculations carried out to determine saturation state of sphalerite in the vent fluids support this hypothesis with isotopically heaviest Zn found in fluids that were calculated to be saturated with respect to sphalerite. We have also measured Zn isotopes in chimney sulfides recovered from a high-temperature (383 °C) and a low-temperature (203 °C) vent at 9–10°N on the EPR and, in both cases, found that the δ⁶⁶Zn of chimney minerals was lighter or similar to the fluid δ⁶⁶Zn. The first measurements of Zn isotopes in hydrothermal fluids have revealed large variations in hydrothermal fluid δ⁶⁶Zn, and suggest that subsurface Zn sulfide precipitation is a primary factor in causing variations in fluid δ⁶⁶Zn. By understanding how chemical processes that occur beneath the seafloor affect hydrothermal fluid δ⁶⁶Zn, Zn isotopes may be used as a tracer for studying hydrothermal processes.     

A preparation zone for volcanic explosions beneath Naka-dake crater,Aso volcano,as inferred from magnetotelluric surveys

The 1st crater of Naka-dake, Aso volcano, is one of the most active craters in Japan, and known to have a characteristic cycle of activity that consists of the formation of a crater lake, drying-up of the lake water, and finally a Strombolian-type eruption. Recent observations indicate an increase in eruptive activity including a decrease in the level of the lake water, mud eruptions, and red hot glows on the crater wall. Temporal variations in the geomagnetic field observed around the craters of Naka-dake also indicate that thermal demagnetization of the subsurface rocks has been occurring in shallow subsurface areas around the 1st crater. Volcanic explosions act to release the energy transferred from magma or volcanic fluids. Measurement of the subsurface electrical resistivity is a promising method in investigating the shallow structure of the volcanic edifices, where energy from various sources accumulates, and in investigating the behaviors of magma and volcanic fluids. We carried out audio-frequency magnetotelluric surveys around the craters of Naka-dake in 2004 and 2005 to determine the detailed electrical structure down to a depth of around 1 km. The main objective of this study is to identify the specific subsurface structure that acts to store energy as a preparation zone for volcanic eruption. Two-dimensional inversions were applied to four profiles across the craters, revealing a strongly conductive zone at several hundred meters depth beneath the 1st crater and surrounding area. In contrast, we found no such remarkable conductor at shallow depths beneath the 4th crater, which has been inactive for 70 years, finding instead a relatively resistive body. The distribution of the rotational invariant of the magnetotelluric impedance tensor is consistent with the inversion results. This unusual shallow structure probably reflects the existence of a supply path of high-temperature volcanic gases to the crater bottom. We propose that the upper part of the conductor identified beneath the 1st crater is mainly composed of hydrothermally altered zone that acts both as a cap to upwelling fluids supplied from deep-level magma and as a floor to infiltrating fluid from the crater lake. The relatively resistive body found beneath the 4th crater represents consolidated magma. These results suggest that the shallow conductor beneath the active crater is closely related to a component of the mechanism that controls volcanic activity within Naka-dake.