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.     

Geochemistry of fluids associated with the 1995–1996 eruption of Mt. Ruapehu, New Zealand: signatures and processes in the magmatic-hydrothermal system

The 1995–1996 eruption of Mt. Ruapehu has provided a number of insights into the geochemical processes operating within the magmatic-hydrothermal system of this volcano. Both pre-eruption degassing of the rising magma and its eventual intrusion into the convective zone of the hydrothermal system beneath the lake were clearly reflected in lake water compositions. The eruptions of September–October 1995 expelled the lake, and provided the first-ever opportunity to characterise gas discharges from this volcano. The fumarolic discharges revealed compositions typical of andesite volcanoes and strong interaction with the enclosing meteoric and hydrothermal system fluids. Some 1.1 MT of SO₂ gas was released from the volcano between September 1995 and December 1996, whereas ca. twice this amount (2.2 MT equivalent SO₂) was erupted as soluble (i.e. leachable) oxyanions of sulphur. Significantly more sulphur was released from the volcano over this period than can be accounted for from the magma volume actually erupted. The evidence suggests that a sizable component of the evolved sulphur was remobilised from the long-lived hydrothermal system within the volcano during the 1995–1996 activity.     

Chemical and isotopic variations in fumarolic discharge and thermal waters at Vulcano Island (Aeolian Islands, Italy) during 1996: evidence of resumed volcanic activity

Gas samples from some fumaroles at ‘La Fossa' crater and Baia di Levante on Vulcano Island and from a diffuse soil gas emission were analysed during 1995–1996, along with water samples from thermal wells in the area of Vulcano Porto. During 1996, we observed a significant increase both in the gas/steam ratio and in the CO₂ concentration, as well as strong variations in δ¹³C_CO2, δD_H2O and δ¹⁸O_H2O of fumarolic gases. These variations are probably related to an increased inflow of deep fluids of magmatic origin. The temperatures of fumaroles did not show remarkable variations except for fumarole F11. In this case, temperature increased by about 80°C from February to August 1996. During the same period, remarkable variations in temperature, phreatic level and chemical and isotopic composition of water were also recorded in one of the geothermal wells in the Vulcano Porto area (Camping Sicilia; T60°C). The observed variations in this well are probably related to a pressure build-up, occurring at least in the surficial part of the system, because of increased gas flux and/or decreased permeability of the fumarolic degassing system. Chemical and isotopic composition of the water showed that during this evolutionary phase, the content of fumarolic condensate in this well was about 80 to 90%. Based on the observation of physical and chemical variables of the Camping Sicilia fluids, during this phase of activity, it is concluded that this area is affected by a phreatic eruption hazard if a volcanic episode with high energy discharge in a limited time span occurs. It follows that this well may be considered as a preferential point for volcanic activity monitoring, both in the case of normal routine surveillance and in the case of inaccessibility to the crater area.     

Gas and hydrogen isotopic analyses of volcanic eruption clouds in Guatemala sampled by aircraft

Gas samples were collected by aircraft entering volcanic eruption clouds of three Guatemalan volcanoes. Gas chromatographic analyses show higher H₂ and S gas contents in ash eruption clouds and lower H₂ and S gases in vaporous gas plumes. H isotopic data demonstrate lighter isotopic distribution of water vapor in ash eruption clouds than in vaporous gas plumes. Most of the H₂O in the vaporous plumes is probably meteoric. The data are the first direct gas analyses of explosive eruptive clouds, and demonstrate that, in spite of atmospheric admixture, useful compositional information on eruptive gases can be obtained using aircraft.     

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.     

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.     

Temporal gravity and elevation changes at Pacaya volcano, Guatemala

Repetitive gravity surveys at Pacaya Volcano from 1975 to 1979 revealed time-dependent changes in the gravity field, which although related to volcanic activity, could not be uniquely attributed to elevation changes or mass redistributions because elevation control was lacking. Elevation control was established in July 1979 using precision leveling. Relative elevation and gravity measurements in June and July of 1979, January 1980 and June 1980 indicate concurrent gravity and elevation changes contemporaneous with variations in eruptive activity. From June 1979 to January 1980, while fumarolic activity was dominant, relative to the most remote station, the volcano deflated by at least 195 mm and the gravity field increased by up to 221 μgal. From January 1980 to June 1980, preceding a Strombolian eruption beginning about June 1980, the volcano inflated by at least 19 mm and the gravity field decreased by up to 231 μgal. Gravity change maps for the intervals of January 1978 to June 1979, June 1979 to January 1980, and January 1980 to June 1980 show areas subject to repeated positive and negative gravity change. Some of those areas coincide with areas of maximum elevation change observed in the June 1979–January 1980 and January 1980–June 1980 intervals; however, gravity changes were observed in areas lacking elevation changes. Adjusting observed gravity changes for elevation changes using a free-air value of −3.086 μgal/cm does not substantially alter the pattern, position, or amplitude of the gravity changes. The relationship between gravity changes, elevation changes, and volcanic activity requires a mechanism producing gravity decreases with little inflation during times of increased eruptive activity, and producing gravity increases with subsidence during times of declining eruptive activity. Such a pattern of changes could be produced by a near-surface magma body in which high-density degassed magma is displaced volume for volume by low-density vesiculated magma during time of increased eruptive activity, and in which loss of gasses by fumarolic activity produces a density increase and a reduction in volume of the magma body during periods of declining eruptive activity. Such a pattern of changes could also be induced by a low-density, vesiculated magma body moving upward in the volcanic pile by piecemeal stoping where the high-density rocks of the volcano are replaced on a volume for volume basis by low-density magma during periods of increasing eruptive activity; and by later density increases and magma body volume reductions accompanying devolatilization and devesiculation during periods of declining eruptive activity. Simple density change and density contrast models involving shallow magma bodies at depths of 100 to 200 m indicate density changes or contrasts of about 0.4 g/cm³ could produce the gravity changes.     

Statistical evaluation of compositional changes in volcanic gas chemistry: a case study

The geochemical analysis of fumarolic gases collected at quiescent and active volcanic systems over time is one of the main tools to understand changes in the state of activity for surveillance and risk assessment. The continuous output of chemical species through fumarolic activity, which characterizes the inter-eruptive intervals, has also a major and general influence on the environment. The mobilization of chemical species due to weathering of volcanic rocks, or the input of gaseous components from fumarolic activity, results in some kind of modification of the environment affecting, in particular, water, soils, and the consequent growth of the plants present in these areas. In this paper, an investigation on the chemical composition of fumarolic gases collected at Vulcano island (Sicily, southern Italy) is performed, with the aim to discover how data changes during the monitored period of time, and to design a strategy for the environmental surveillance of volcanic systems taking into account the nature of the analyzed data. In order to summarize the contribution of all the components that can affect the chemical composition of volcanic gases, a multivariate statistical approach appears to be suitable. Since many of those methods assume independent observations, the possible presence of time-dependent structures should be carefully verified. In this framework, given the compositional nature of geochemical data, we have applied recent theoretical and practical developments in the field of compositional data analysis to work in the correct sample space and to isolate groups of parts responsible for significant changes in the gas chemistry. The proposed approach can be generalized to the investigation of complex environmental systems.     

Fumarolic activity of Avachinsky and Koryaksky volcanoes, Kamchatka, from 1993 to 1994

 Volcanic gas and condensate samples were collected in 1993–1994 from fumaroles of Koryaksky and Avachinsky, basaltic andesite volcanoes on the Kamchatka Peninsula near Petropavlovsk–Kamchatsky. The highest-temperature fumarolic discharges, 220  °C at Koryaksky and 473  °C at Avachinsky, are water-rich (940–985 mmol/mol of H₂O) and have chemical and isotopic characteristics typical of Kamchatka–Kurile, high- and medium-temperature volcanic gases. The temperature and chemical and water isotopic compositions of the Koryaksky gases have not changed during the past 11 years. They represent an approximate 2 : 1 mixture of magmatic and meteoric end members. Low-temperature, near-boiling-point discharges of Avachinsky Volcano are water poor (≈880 mmol/mol); Their compositions have not changed since the 1991 eruption, and are suggested to be derived from partially condensed magmatic gases at shallow depth. Based on a simple model involving mixing and single-step steam separation, low water and high CO₂ contents, as well as the observed Cl concentration and water isotopic composition in low-temperature discharges, are the result of near-surface boiling of a brine composed of the almost pure condensed magmatic gas. High methane content in low-temperature Avachinsky gases and the 220  °C Koryaksky fumarole, low C isotopic ratio in CO₂ at Koryaksky (–11.8‰), and water isotope data suggest that the "meteoric" end member contains considerable amounts of the regional methane-rich thermal water discovered in the vicinity of both volcanoes. Received: 2 May 1996 / Accepted: 5 November 1996     

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.     

Genesis and evolution of the fumaroles of vulcano (Aeolian Islands,Italy): a geochemical model

A geochemical model explaining the presence of fumaroles having different gas composition and temperature at the top of the crater and along the northeastern coast of Vulcano island is proposed. A pressurized biphase (liquid-vapor) reservoir at the depth of about 2 km is hypothesized. Energy and mass balance sheets controlP-T conditions in the system.P-T must vary along a boiling curve of brine as liquid is present. The CO₂ content in the steam is governed by the thermodynamic properties of the fluids in the H₂-NaCl-CO₂ system. On the assumption that oxygen fugacity in the system is between the HM-FMQ oxygen buffers, observed SO₂/H₂S, CO₂/CO, CO/CH₄ ratios in the fumarolic gases at the Fossa crater appear in equilibrium with a temperature higher than that observed, such as may exist at depth. The more reduced gas phases present on the sea-side may result from re-equilibrium processes in shallower aquifers. The suggested model would help in monitoring changes in volcanic activity by analyzing fumarolic gases.     

Field measurements of volcanic gases. Vulcano Island (Italy), Kilauea (Hawaii,U.S.A.), Merapi (Java,Indonesia)

A field gas chromatograph, built in 1978, was used in the field to directly analyse volcanic gases before water vapor condensation. Tested in Vulcano (Italy), Kilauea (Hawaii) and Merapi (Indonesia), this field measurement technique provides the actual composition of the volcanic gas mixture. The technique avoids the depletion of sulfur gases and the dissolution of the acid gases in the condensed water during the cooling. Thus the mixture of H₂S and SO₂ in fumarolic and high temperature gases (up to 819°C) in equilibrium at the emission temperature was examined.     

Fluid geochemistry of Montserrat Island,West Indies

 Two geochemical surveys carried out in March 1991 and September 1992 revealed the existence of a hydrothermal system in the southern portion of Montserrat Island, below Soufrière Hills Volcano. This conclusion is supported by the presence of: (a) the thermal springs of Plymouth which are fed by deep Na–Cl waters (Cl concentration ∼25 000 mg/kg, temperature ca. 250  °C) mixed with shallow steam-heated waters; (b) the four fumarolic fields of Galway's Soufrière, Gages Upper Soufrière, Gages Lower Soufrière, and Tar River Soufrière, where acid to neutral, steam-heated waters are present together with several fumarolic vents, discharging vapors formed through boiling of hydrothermal aqueous solutions. Involvement of magmatic fluids in the recharge of the hydrothermal aquifers is suggested by: (a) the high ³He/⁴He ratios of fumarolic fluids, i.e., 8.2 R_A at Galway's Soufrière and 5.9 R_A at Gages Lower Soufrière; (b) the δD and δ¹⁸O values of Na–Cl thermal springs and steam condensates, indicating the involvement of arc-type magmatic water in the formation of deep geothermal liquids; and (c) the CH₄/CO₂ ratios of fumarolic fluids, which are lower than expected for equilibrium with the FeO–FeO_1.5 hydrothermal rock buffer, but being shifted towards the SO₂–H₂S magmatic gas buffer. Received: 26 March 1996 / Accepted: 19 July 1996     

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     

Evolution of fluid geochemistry at the Turrialba volcano (Costa Rica) from 1998 to 2008

Turrialba (10°02′N, 83°45′W) is a 3,349-m high stratovolcano belonging to the Holocene “Cordillera Central” volcanic belt of Costa Rica. The summit consists of three EW-oriented craters (East, Central, and West). Since its last eruptive phase (1864–1866), the Central and West craters have displayed modest fumarolic activity, with outlet temperatures clustering around 90°C. In 2001, seismic swarms, ground deformation, and increasing fumarolic activity occurred. From 2005 to 2008, new fumarolic vents opened between and within the Central and West craters, and along the western and southwestern outer flanks of the volcanic edifice. These physical changes were accompanied by a drastic modification in the gas chemistry that can be divided in three stages: (1) hydrothermal (from 1998 to autumn 2001), characterized by the presence of H₂O, CO₂, H₂S, and, to a very minor extent, HCl and HF; (2) hydrothermal/magmatic (autumn 2001–2007), with the appearance of SO₂ and a significant increase of HCl and HF; and (3) magmatic-dominated (2007–2008), characterized by increased SO₂ content, SO₂/H₂S > 100, and temperatures up to 282°C. Accordingly, gas equilibrium in the CO₂-CH₄-H₂ system suggests a progressive evolution of the deep fluid reservoir toward higher temperatures and more oxidizing conditions. The chemical–physical modifications of Turrialba in the last decade can be interpreted as part of a cyclic mechanism controlling the balance between the hydrothermal and the magmatic systems. Nevertheless, the risk of rejuvenation of the volcanic activity cannot be excluded, and an appropriate seismic, ground deformation, and geochemical monitoring program is highly recommended. Turrialba lies at a distance of 35 and 15 km from San José and Cartago, respectively, the two largest cities in Costa Rica.     

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.     

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.     

Diffuse emission of CO2 from the Fossa crater,Vulcano Island (Italy)

 Numerous measurements of CO₂ degassing from the soil, carried out with the accumulation chamber method, indicate that in the period April–July 1995 the upper part of the Fossa cone released a total output of 200 t d^–1 of CO₂, which corresponds to approximately 1000 t d^–1 of steam. These large amounts of fluids are of the same order of magnitude as those released by the high temperature fumarolic field located inside the crater. The spatial distribution of soil gas fluxes shows that the main structures releasing CO₂ are the inner slopes of the crater and a NW–SE line, located NE of the crater rim, which correspond to the main direction of Vulcano Island active faults. The comparison of the φCO₂ maps with the soil temperature distribution, derived from both direct measurements and airborne infrared images, indicates the occurrence of extensive condensation of fumarolic steam within the upper part of the Fossa cone, whose total amount is comparable to the rainfall budget. Part of the condensate which originates from this process contributes to the recharge of the phreatic aquifer of Porto Plain, modifying the chemical and isotopic composition of the groundwater. Received: 1 September 1995 / Accepted: 8 January 1996     

Presence of native gold and tellurium in the active high-sulfidation hydrothermal system of the La Fossa volcano (Vulcano, Italy)

Grains of native gold and tellurium were found in siliceous hydrothermally altered rocks in the high-temperature (170–540°C) fumarolic field of the La Fossa volcano (Island of Vulcano). In addition to Au and Te, Pb–Bi sulfides (cannizzarite) and Tl-bromide chloride were found as sublimates in the hottest fumarolic vents of the crater rim. The chemical composition of altered rocks associated with sublimate deposition indicate the presence of a significant concentration of Te (up to 75 ppm), while gold concentrations are very low (<9 ppb). Pb, Bi and Tl are strongly enriched in the hottest and less oxidized fumarolic vents, reaching concentrations of 2186, 146 and 282 ppm, respectively. These elements are transported (generally as chloride complexes) to the surface by volcanic gases, and several of these (Bi, Te, Tl) are originated from magma degassing. The silicic alteration is produced by the flow of fluids with pH<2. High acidity results from introduction of magmatic gases such as SO₂, HCl and HF released by the shallow magmatic reservoir of La Fossa volcano. The silicic alteration found at Vulcano may represent an early stage of the `vuggy silica' facies which characterizes the high-sulfidation epithermal ore deposits, confirming the analogies existing between this type of ore deposit and magmatic-hydrothermal systems associated with island-arc volcanoes.     

Lead isotope composition of the sublimates from the fumaroles of Vulcano (Aeolian Islands,Italy): inferences on the deep fluid circulation

The fumarolic fluids of Vulcano (Aeolian Islands, Italy) consist of a mixture of both deep and shallow components. The final products, the fumarolic gases and the sublimates associated with them, provide information on the complex interactions that occur at depth. As radiogenic isotopes do not undergo fractionation after they are incorporated in a fumarolic gas, they can be used directly to characterize the components that mixed. Lead isotopes are particularly suitable, because seawater, which plays an important part in the formation of the fumarolic fluids of Vulcano, contains only negligible amounts of it (10^-12 g/g). Therefore, the lead present in the fumarolic gases (and sublimates) is derived from the magmatic component and a water-rock interaction process. The lead isotope compositions of the lead sulfosalt sublimates collected from the Fossa Crater of Vulcano in 1924, and between 1989 and 1993, are given. The lead isotope ratios of most of the samples are the same within the range of analytical error, regardless of their collection date. The only samples that display slight variations are those collected in 1993. On the whole, the compositional trend of the lead isotopes of the sublimates coincides with that of the latitic-rhyolitic activity of Fossa and differs substantially from that of the pre-Fossa trachy-basaltic activity. The lead composition of the sublimates is very different from that of the Calabrian basement rocks. The data presented here show that the magma presently degassing at Vulcano has the same lead isotopic composition as the products of the recent activity of Fossa, whereas the fumarolic fluid circulation of Vulcano has not involved basement rocks similar to the Calabrian metasediments.