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.     

Sulfur dioxide emissions from Popocatépetl volcano (Mexico): case study of a high-emission rate, passively degassing erupting volcano

Popocatépetl volcano in central Mexico has been erupting explosively and effusively for almost 4 years. SO₂ emission rates from this volcano have been the largest ever measured using a COSPEC. Pre-eruptive average SO₂ emission rates (2–3 kt/d) were similar to the emission rates measured during the first part of the eruption (up to August 1995) in contrast with the effusive–explosive periods (March 1996–January 1998) during which SO₂ emission rates were higher by a factor of four (9–13 kt/d). Based on a chronology of the eruption and the average SO₂ emission rates per period, the total SO₂ emissions (up to 1 January 1998) are estimated to be about 9 Mt, roughly half as much as the SO₂ emissions from Mount Pinatubo in a shorter period. Popocatépetl volcano is thus considered as a high-emission rate, passively degassing eruptive volcano. SO₂ emission rates and SO₂ emissions are used here to make a mass balance of the erupted magma and related gases. Identified excess SO₂ is explained in terms of continuous degassing of unerupted magma and magma mixing. Fluctuations in SO₂ emission rate may be a result of convection and crystallization in the chamber or the conduits, cleaning and sealing of the plumbing system, and/or SO₂ scrubbing by the hydrothermal system.     

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.     

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.     

Environmental hazards of fluoride in volcanic ash: a case study from Ruapehu volcano, New Zealand

The vent-hosted hydrothermal system of Ruapehu volcano is normally covered by a c. 10 million m³ acidic crater lake where volcanic gases accumulate. Through analysis of eruption observations, granulometry, mineralogy and chemistry of volcanic ash from the 1995–1996 Ruapehu eruptions we report on the varying influences on environmental hazards associated with the deposits. All measured parameters are more dependent on the eruptive style than on distance from the vent. Early phreatic and phreatomagmatic eruption phases from crater lakes similar to that on Ruapehu are likely to contain the greatest concentrations of environmentally significant elements, especially sulphur and fluoride. These elements are contained within altered xenolithic material extracted from the hydrothermal system by steam explosions, as well as in residue hydrothermal fluids adsorbed on to particle surfaces. In particular, total F in the ash may be enriched by a factor of 6 relative to original magmatic contents, although immediately soluble F does not show such dramatic increases. Highly soluble NaF and CaSiF₆ phases, demonstrated to be the carriers of ‘available’ F in purely magmatic eruptive systems, are probably not dominant in the products of phreatomagmatic eruptions through hydrothermal systems. Instead, slowly soluble compounds such as CaF₂, AlF₃ and Ca₅(PO₄)₃F dominate. Fluoride in these phases is released over longer periods, where only one third is leached in a single 24-h water extraction. This implies that estimation of soluble F in such ashes based on a single leach leads to underestimation of the F impact, especially of a potential longer-term environmental hazard. In addition, a large proportion of the total F in the ash is apparently soluble in the digestive system of grazing animals. In the Ruapehu case this led to several thousand sheep deaths from fluorosis.     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Radionuclides and sulfur content in Mount Etna plume in 1983–1995: new constraints on the magma feeding system

Radionuclide activities (²¹⁰Pb, ²¹⁰Bi, ²¹⁰Po) were investigated in Mount Etna plume from 1983 to 1995. At SE crater the long-term observation (12 years) of the ²¹⁰Po/²¹⁰Pb ratio shows that it can behave as a degassing vent not directly related to the main magma reservoir depending on the magma level inside the volcano. Since 1992, the simultaneous determination of radionuclides and sulfur in the main plume results in new constraints on the degassing model of Lambert et al. (Earth Planet. Sci. Lett., 76 (1986) 185). The ²¹⁰Po/SO₂ and ²¹⁰Pb/SO₂ ratios enable us to identify two sources of ²¹⁰Po in the plume: one is magmatic, correlated with SO₂, the other one is an additional component issued from the decay of ²¹⁰Pb in the shallow degassing cell, and depends directly on the residence time of the gases before their emission. Estimations of the volume of degassing magma, the residence time of the gases and the proportion of undegassed magma renewing the shallow degassing cell are given for the period 1992–1995. During the 1992 eruption, the rate of degassing magma volume is estimated to have been as high as 5×10⁶ m³/day, and the volume of the shallow degassing magma reservoir about 0.5 km³. In 1994 and 1995 the rate of non-erupted degassing magma volume was estimated to have been about 0.18 km³/year. During the entire 1983–1995 period, only 15–20% of the degassed magma was erupted.     

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     

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.     

Degassing patterns of Tungurahua volcano (Ecuador) during the 1999–2006 eruptive period,inferred from remote spectroscopic measurements of SO2 emissions

This paper presents the results of 7 years (Aug. 1999–Oct. 2006) of SO₂ gas measurements during the ongoing eruption of Tungurahua volcano, Ecuador. From 2004 onwards, the operation of scanning spectrometers has furnished high temporal resolution measurements of SO₂ flux, enabling this dataset to be correlated with other datasets, including seismicity. The emission rate of SO₂ during this period ranges from less than 100 to 35,000 tonnes/day (t d^− 1) with a mean daily emission rate of 1458 t d^− 1 and a standard deviation of ± 2026 t d^− 1. Average daily emissions during inferred explosive phases are about 1.75 times greater than during passive degassing intervals. The total amount of sulfur emitted since 1999 is estimated as at least 1.91 Mt, mostly injected into the troposphere and carried westwards from the volcano. Our observations suggest that the rate of passive degassing at Tungurahua requires SO₂ exsolution of an andesitic magma volume that is two orders of magnitude larger than expected for the amount of erupted magma. Two possible, and not mutually exclusive, mechanisms are considered here to explain this excess degassing: gas flow through a permeable stagnant-magma-filled conduit and gas escape from convective magma overturning in the conduit. We have found that real-time gas monitoring contributes significantly to better eruption forecasting at Tungurahua, because it has provided improved understanding of underlying physical mechanisms of magma ascent and eruption.     

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     

SO2 emissions at Mt. Etna with particular reference to the period 1993–1995

The variations in sulfur dioxide (SO₂) emission from the Summit Craters of Mt. Etna were determined, with particular reference to the period 1993–1995. Vehicle-based weekly measurements of SO₂ flux, using a correlation spectrometer (COSPEC), suggest new input of magma into the main feeder system of the volcano between 1993 and 1995. Minimal flux values (<1000 t/day) preceded the two eruptive events in the period 1987–1995. Only approximately 9.5% of the magma that contributed the SO₂ emission was erupted during the same period. Received: 3 November 1997 / Accepted: 21 September 1998     

Geochemistry and mineralogy of the phonolite lava lake,Erebus volcano,Antarctica: 1972–2004 and comparison with older lavas

Mount Erebus, Antarctica, is a large (3794 m) alkaline open-conduit stratovolcano that hosts a vigorously convecting and persistently degassing lake of anorthoclase phonolite magma. The composition of the lake was investigated by analyzing glass and mineral compositions in lava bombs erupted between 1972 and 2004. Matrix glass, titanomagnetite, olivine, clinopyroxene, and fluor-apatite compositions are invariant and show that the magmatic temperature (∼ 1000°C) and oxygen fugacity (ΔlogFMQ = − 0.9) have been stable. Large temperature variations at the lake surface (~ 400–500°C) are not reflected in mineral compositions. Anorthoclase phenocrysts up to 10 cm in length feature a restricted compositional range (An_10.3–22.9Ab_62.8–68.1Or_11.4–27.2) with complex textural and compositional zoning. Anorthoclase textures and compositions indicate crystallization occurs at low degrees of effective undercooling. We propose shallow water exsolution causes crystallization and shallow convection cycles the anorthoclase crystals through many episodes of growth resulting in their exceptional size. Minor variations in eruptive activity from 1972 to 2004 are decoupled from magma compositions. The variations probably relate to changes in conduit geometry within the volcano and/or variable input of CO₂-rich volatiles into the upper-level magma chamber from deeper in the system.     

Magmatic gas scrubbing: implications for volcano monitoring

Despite the abundance of SO_2(g) in magmatic gases, precursory increases in magmatic SO_2(g) are not always observed prior to volcanic eruption, probably because many terrestrial volcanoes contain abundant groundwater or surface water that scrubs magmatic gases until a dry pathway to the atmosphere is established. To better understand scrubbing and its implications for volcano monitoring, we model thermochemically the reaction of magmatic gases with water. First, we inject a 915°C magmatic gas from Merapi volcano into 25°C air-saturated water (ASW) over a wide range of gas/water mass ratios from 0.0002 to 100 and at a total pressure of 0.1 MPa. Then we model closed-system cooling of the magmatic gas, magmatic gas-ASW mixing at 5.0 MPa, runs with varied temperature and composition of the ASW, a case with a wide range of magmatic–gas compositions, and a reaction of a magmatic gas–ASW mixture with rock. The modeling predicts gas and water compositions, and, in one case, alteration assemblages for a wide range of scrubbing conditions; these results can be compared directly with samples from degassing volcanoes. The modeling suggests that CO_2(g) is the main species to monitor when scrubbing exists; another candidate is H₂S_(g), but it can be affected by reactions with aqueous ferrous iron. In contrast, scrubbing by water will prevent significant SO_2(g) and most HCl_(g) emissions until dry pathways are established, except for moderate HCl_(g) degassing from pH<0.5 hydrothermal waters. Furthermore, it appears that scrubbing will prevent much, if any, SO_2(g) degassing from long-resident boiling hydrothermal systems. Several processes can also decrease or increase H_2(g) emissions during scrubbing making H_2(g) a poor choice to detect changes in magma degassing.We applied the model results to interpret field observations and emission rate data from four eruptions: (1) Crater Peak on Mount Spurr (1992) where, except for a short post-eruptive period, scrubbing appears to have drastically diminished pre-, inter-, and post-eruptive SO_2(g) emissions, but had much less impact on CO_2(g) emissions. (2) Mount St. Helens where scrubbing of SO_2(g) was important prior to and three weeks after the 18 May 1980 eruption. Scrubbing was also active during a period of unrest in the summer of 1998. (3) Mount Pinatubo where early drying out prevented SO_2(g) scrubbing before the climactic 15 June 1991 eruption. (4) The ongoing eruption at Popocatépetl in an arid region of Mexico where there is little evidence of scrubbing.In most eruptive cycles, the impact of scrubbing will be greater during pre- and post-eruptive periods than during the main eruptive and intense passive degassing stages. Therefore, we recommend monitoring the following gases: CO_2(g) and H₂S_(g) in precursory stages; CO_2(g), H₂S_(g), SO_2(g), HCl_(g), and HF_(g) in eruptive and intense passive degassing stages; and CO_2(g) and H₂S_(g) again in the declining stages. CO_2(g) is clearly the main candidate for early emission rate monitoring, although significant early increases in the intensity and geographic distribution of H₂S_(g) emissions should be taken as an important sign of volcanic unrest and a potential precursor. Owing to the difficulty of extracting SO_2(g) from hydrothermal waters, the emergence of >100 t/d (tons per day) of SO_2(g) in addition to CO_2(g) and H₂S_(g) should be taken as a criterion of magma intrusion. Finally, the modeling suggests that the interpretation of gas-ratio data requires a case-by-case evaluation since ratio changes can often be produced by several mechanisms; nevertheless, several gas ratios may provide useful indices for monitoring the drying out of gas pathways.     

Petrologic investigations of the 1995 and 1996 eruptions of Ruapehu volcano, New Zealand: formation of discrete and small magma pockets and their intermittent discharge

 Ruapehu volcano erupted intermittently between September and November 1995, and June and July 1996, producing juvenile andesitic scoria and bombs. The volcanic activity was characterized by small, sequential phreatomagmatic and strombolian eruptions. The petrography and geochemistry of dated samples from 1995 (initial magmatic eruption of 18 September 1995, and two larger events on 23 September and 11 October), and from 1996 (initial and larger eruptions on 17–18 June) suggest that episodes of magma mixing occurred in separate magma pockets within the upper part of the magma plumbing system, producing juvenile andesitic magma by mixing between relatively high (1000–1200  °C)- and low (∼1000  °C)- temperature (T) end members. Oscillatory zoning in pyroxene phenocrysts suggests that repeated mixing events occurred prior to and during the 1995 and 1996 eruptions. Although the 1995 and 1996 andesitic magmas are products of similar mixing processes, they display chronological variations in phenocryst clinopyroxene, matrix glass, and whole-rock compositions. A comparison of the chemistry of magnesian clinopyroxene in the four tephras indicates that, from 18 September through June 1996, the tephras were derived from at least two discrete high-temperature (high-T) batches of magma. Crystals of magnesian clinopyroxene in the 23 September and 11 October tephras appear to be derived from different high-T magma batches. Whole-rock and matrix-glass compositions of all tephras are consistent with their derivation from distinct mixed melts. We propose that, prior to 1995 there was a shallow low-temperature (low-T) magma storage system comprising crystal-rich mush and remnant magma from preceding eruptive episodes. Crystal clots and gabbroic inclusions in the tephras attest to the existence of relict crystal mush. At least two discrete high-T magmas were then repeatedly injected into the mush zone, forming discrete and mixed magma pockets within the shallow system. The intermittent 1995 and 1996 eruptions sequentially tapped these magma pockets. Received: 1 April 1998 / Accepted: 22 December 1998     

Surface deformation at the Krafla volcano,North Iceland, 1982–1992

Extensive measurements of ground deformation at the Krafla volcano, Iceland, have been made since the beginning in 1975 of a series of eruptions and intrusions into the fissure system that extends north and south of the volcano. I concentrate on measurements before and after the eruption of September 1984, the last event of this series when the largest volume of lava was erupted. The patterns of ground deformation associated with the 1984 eruption, determined by precision levelling, electronic distance measurements and lake level observations, were similar to earlier intrusions and eruptions, in that the surface of the volcano subsided and the fissure system widened as magma moved laterally from a shallow central reservoir into the fissure system. The shallow magma reservoir of Krafla continued to expand for about five years after the eruption, but a slow subsidence of the central area began in 1989. Besides the presence of an inflating and deflating shallow magma reservoir at a depth of 2.5 km beneath the Krafla caldera, another inflating magma reservoir may exist at much greater depth below Krafla. The accumulation of compressive strain by numerous rift intrusions and eruptions since 1975 along the flanks of the north-south Krafla fissure swarm is being released slowly and will probably be reflected in the results of deformation measurements near Krafla for the next several decades. The total horizontal extension of the Krafla rift system in 1975–1984 was about 9 m, equal to about 500 years of constant plate divergence. The extension is twice the accumulated divergence since previous rifting events and eruptions in 1724–1729     

CO2 output and δ13C(CO2) from Mount Etna as indicators of degassing of shallow asthenosphere

 An estimated average CO₂ output from Etna's summit craters in the range of 13±3 Mt/a has recently been determined from the measured SO₂ output and measured CO₂/SO₂ molar ratios. To this amount the CO₂ output emitted diffusely from the soil (≈ 1 Mt/a) and the amount of CO₂ dissolved in Etna's aquifers (≈ 0.25 Mt/a) must be added. Data on the solubility of CO₂ in Etnean magmas at high temperature and pressure allow the volume of magma involved in the release of such an amount of this gas to be estimated. This volume of magma (≈ 0.7 km³/a) is approximately 20 times greater than the volume of magma erupted annually during the period 1971–1995. On the basis of C-isotopic data of CO₂ collected in the Etna area and of new hypotheses on the source of Mediterranean magmas, significant contributions of CO₂ from non-magmatic sources to the total output from Etna are unlikely. Such large outputs of CO₂ and also of SO₂ from Etna could be due to an anomalously shallow asthenosphere beneath the volcano that allows a continuous escape of gases toward the surface, even without migration of magma. Received: 7 August 1996 / Accepted: 9 November 1996     

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.     

Fumarolic gases at Mombacho volcano (Nicaragua): presence of magmatic gas species and implications for volcanic surveillance

Mombacho is a deeply dissected volcano belonging to the Quaternary volcanic chain of Nicaragua. The southern, historic collapse crater (El Crater) currently hosts a fumarolic field with a maximum temperature of 121°C. Chemical and isotopic data from five gas-sampling field campaigns carried out in 2002, 2003 and 2005 highlight the presence of high-temperature gas components (e.g. SO₂, HCl and HF), which indicate a significant contribution of juvenile magmatic fluids to the hydrothermal system feeding the gas discharges. This is strongly supported by the mantle-derived helium and carbon isotopic signatures, although the latter is partly masked by either a sedimentary subduction-related or a shallow carbonate component. The observed chemical and isotopic composition of the Mombacho fluids seems to indicate that this volcanic system, although it has not experienced eruptive events during the last centuries, can be considered active and possibly dangerous, in agreement with the geophysical data recorded in the region. Systematic geochemical monitoring of the fumarolic gas discharges, coupled with a seismic and ground deformation network, is highly recommended in order to monitor a possible new eruptive phase.     

Remarkable geochemical changes and degassing at Voui crater lake,Ambae volcano,Vanuatu

Ambae (also known as Aoba), is a 38 × 16 km² lozenge-shaped island volcano with a coastal population of around 10 000. At the summit of the volcano is lake Voui — one of the largest active crater lakes worldwide, with 40 × 10⁶ m³ of acidic water perched 1400 m a.s.l. After more than 300 years of dormancy, Ambae volcano reawakened with phreatic eruptions through Voui in 1995, and culminating in a series of surtseyan eruptions in 2005, followed by a rapid and spectacular colour change of the lake from light blue to red in 2006. Integrating lake water chemistry with new measurements of SO₂ emissions from the volcano during the 2005–2006 eruptive period helps to explain the unusual and spectacular volcanic activity of Ambae — initially, a degassed magma approached the lake bed and triggered the surtseyan eruption. Depressurization of the conduit facilitated ascent of volatile-rich magma from the deeper plumbing system. The construction of a cone during eruption and the high degassing destabilised the equilibrium of lake stratification leading to a limnic event and subsequently the spectacular colour change.