The hydrothermal system of Volcan Puracé, Colombia

This paper presents chemical and isotopic data for thermal waters, gases and S deposits from Volcan Puracé (summit elevation 4600 m) in SW Colombia. Hot gas discharges from fumaroles in and around the summit crater, and thermal waters discharge from three areas on its flanks. The waters from all areas have D values of-75±1, indicating a single recharge area at high elevation on the volcano. Aircorrected values of³He/⁴He in thermal waters range from 3.8 to 6.7 R_A, and approach those for crater fumarole gas (6.1–7.1 R_A), indicating widespread addition of magmatic volatiles. An economic S deposit (El Vinagre) is being mined in the Rio Vinagre fault zone at 3600 m elevation. Sulfur isotopic data are consistent with a magmatic origin for S species in thermal waters and gases, and for the S ore deposit. Isotopic equilibration between S species may have occurred at 220±40°C, which overlaps possible equilibration temperatures (170±40°C) determined by a variety of other geothermometers for neutral thermal waters. Apparent CH₄–CO₂ equilibration temperatures for gases from thermal springs (400±50°C) and crater fumaroles (520±60°C) reflect higher temperatures deeper in the system. Hot magmatic gas ascending through the Rio Vinagre fault zone is though to have precipitated S and generated thermal waters by interaction with descending meteoric waters.     

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

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

Variation in noble gas isotopic composition of gas samples from the Aegean arc, Greece

In contrast to most other arcs with oceanic plate subduction, the Aegean arc is characterized by continent–continent subduction. Noble gas abundances and isotopic compositions of 45 gas samples have been determined from 6 volcanoes along the arc, 2 islands in the back-arc region and 7 sites in the surrounding areas. The ³He/⁴He ratios of the samples ranged from 0.027R_A to 6.2R_A (R_A denotes the atmospheric ³He/⁴He ratio of 1.4×10⁻⁶), demonstrating that even the maximum ³He/⁴He ratio in the region is significantly lower than the maximum ratios of most oceanic subduction systems, which are equal to the MORB value of 8±1 R_A. Regional variations in the ³He/⁴He ratio were observed both along and across the arc. The maximum ³He/⁴He ratio was obtained from Nisyros volcano located in the eastern end of the arc, and the ratio decreased westward possibly reflecting the difference in potential degree of crustal assimilation or the present magmatic activity in each volcano. Across the volcanic arc, the ³He/⁴He ratio decreased with an increasing distance from the arc front, reaching a low ratio of 0.063R_A in Macedonia, which suggested a major contribution of radiogenic helium derived from the continental crust. At Nisyros, a temporal increase in ³He/⁴He ratio due to ascending subsurface magma was observed after the seismic crisis of 1995–1998 and mantle neon was possibly detected. The maximum ³He/⁴He ratio (6.2R_A) in the Aegean region, which is significantly lower than the MORB value, is not probably due to crustal assimilation at shallow depth or addition of slab-derived helium to MORB-like mantle wedge, but inherent characteristics of the subcontinental lithospheric mantle (SCLM) beneath the Aegean arc.     

Gas geochemistry of the Valles caldera region, New Mexico and comparisons with gases at Yellowstone, Long Valley and other geothermal systems

Noncondensible gases from hot springs, fumaroles, and deep wells within the Valles caldera geothermal system (210–300°C) consist of roughly 98.5 mol% CO₂, 0.5 mol% H₂S, and 1 mol% other components. ³He/⁴He ratios indicate a deep magmatic source (R/R_a up to 6) whereas δ¹³C–CO₂ values (−3 to −5‰) do not discriminate between a mantle/magmatic source and a source from subjacent, hydrothermally altered Paleozoic carbonate rocks. Regional gases from sites within a 50-km radius beyond Valles caldera are relatively enriched in CO₂ and He, but depleted in H₂S compared to Valles gases. Regional gases have R/R_a values ≤1.2 due to more interaction with the crust and/or less contribution from the mantle. Carbon sources for regional CO₂ are varied. During 1982–1998, repeat analyses of gases from intracaldera sites at Sulphur Springs showed relatively constant CH₄, H₂, and H₂S contents. The only exception was gas from Footbath Spring (1987–1993), which experienced increases in these three components during drilling and testing of scientific wells VC-2a and VC-2b. Present-day Valles gases contain substantially less N₂ than fluid inclusion gases trapped in deep, early-stage, post-caldera vein minerals. This suggests that the long-lived Valles hydrothermal system (ca. 1 Myr) has depleted subsurface Paleozoic sedimentary rocks of nitrogen. When compared with gases from many other geothermal systems, Valles caldera gases are relatively enriched in He but depleted in CH₄, N₂ and Ar. In this respect, Valles gases resemble end-member hydrothermal and magmatic gases discharged at hot spots (Galapagos, Kilauea, and Yellowstone).     

Helium-isotope systematics at Nevado del Ruiz volcano, Colombia: implications for the volcanic hydrothermal system

We have collected 14 water and gas samples from 9 thermal springs and gas vents near Nevado del Ruiz volcano, Colombia. The ³He/⁴He and ⁴He/²⁰Ne ratios vary significantly from 0.98 R_atm (where R_atm is the atmospheric ³He/⁴He ratio of 1.4 × 10⁻⁶) to 6.30 R_atm, and from 0.37 to 7.0, respectively. The ³He/⁴He ratio (corrected for air contamination) decreases with increasing distance from the central crater of the volcano to the sampling site. The trend is very similar to that observed at Ontake volcano, Japan. A hydrodynamic porous-media dispersion model can explain the ³He/⁴He trend. The temporal variations in the ³He/⁴He ratio at four sites provide useful information on the apparent velocity of the magmatic fluid flow brought on by a volcanic eruption. The estimated value of several tens m day⁻¹ agrees well with the inferred velocity of flow in Oshima volcano, Japan and is comparable to the largest rate of groundwater movement in a deep sedimentary basin.     

Geochemical investigations of submarine volcanic exhalations to the east of Panarea, Aeolian Islands, Italy

Results are presented on scubadiving investigations carried out on thermal manifestations in the area of Panarea (Aeolian Islands). The area investigated falls inside a caldera which extends from the main island to the group of islets located to the northeast. The distribution of the gaseous manifestations is regulated by the NE-SW, NW-SE and N-S regional tectonic directrices, through which the more recent basic magma intruded, giving rise to dikes and pillow lavas. f_O2-temperature relation of the gases sampled in the investigated area was calculated to be: logf_O2 = 11−24,593/T which indicates that a buffering mechanism acted on the gases as they cooled down during their ascent. The high ³He/⁴He ratio (6 × 10⁻⁶) and the δ¹³C = −3.2%. (PDB), suggest the presence of a magmatic component in the gas feeding the investigated manifestations. The above relations and the almost constant high He/N₂ ratio suggest that all the fumaroles are fed by the same deep hot fluids. On the basis of both the chemical characters of the fluids and the geothermo-barometric data, a deep geothermal body, having a temperature of about 240°C, is recognized. Two other shallower thermal aquifers, with a temperature of 170–210°C, are identified. A circulation pattern of the geothermal fluids is also proposed. On the basis of calculations regarding the convective energy released by the geothermal system of Panarea, and the magmatic mass responsible for the positive gravimetric anomaly of the area, it was estimated that the last volcanic activity took place less then 10,000 years ago.     

Helium isotopic ratio in Vulcano island fumaroles: temporal variations in shallow level mixing and deep magmatic supply

Intensive gas emanations occur throughout the island of Vulcano, Italy. Sharp fluctuations recorded in the crater gas composition suggest the presence of two separate volcanic reservoirs and continuous mixing with another source, “crustal” waters. This mixing differs between the beach and crater fumaroles. Gas samples from three crater fumaroles with temperatures ranging from 200 to 550 ° C were sampled repeatedly over a one year period. During the same interval of time, six samples from submarine and subaerial beach fumaroles and water well gases were also sampled. Gases from one crater fumarole (F5) showed variations of (³He/⁴He)_fumarole to (³He/⁴He)_air between 5 and 6 correlated with variations of several chemical species. High ³He/⁴He ratios for the beach fluids, similar to those of crater fluids, suggest the existence of a unique large magmatic reservoir at depth feeding both the crater and beach intermediate reservoirs. However, temporal changes clearly indicate variable degrees of fluids mixing, and the geographic distribution of the ³He/⁴He ratios as well as the chemical composition of the fluids suggest the existence between the magma reservoir and the surface of two intermediate different reservoirs, independently related to crater and to beach fumaroles.     

A model of diffuse degassing at three subduction-related volcanoes

2 and δ¹³C in soil gas were measured at three active subduction-related stratovolcanoes (Arenal and Poás, Costa Rica; Galeras, Colombia). In general, Rn, CO₂ and δ¹³C values are higher on the lower flanks of the volcanoes, except near fumaroles in the active craters. The upper flanks of these volcanoes have low Rn concentrations and light δ¹³C values. These observations suggest that diffuse degassing of magmatic gas on the upper flanks of these volcanoes is negligible and that more magmatic degassing occurs on the lower flanks where major faults and greater fracturing in the older lavas can channel magmatic gases to the surface. These results are in contrast to findings for Mount Etna where a broad halo of magmatic CO₂ has been postulated to exist over much of the edifice. Differences in radon levels among the three volcanoes studied here may result from differences in age, the degree of fracturing and faulting, regional structures or the level of hydrothermal activity. Volcanoes, such as those studied here, act as plugs in the continental crust, focusing magmatic degassing towards crater fumaroles, faults and the fractured lower flanks. Received: 16 December 1997 / Accepted: 27 January 2000     

Tritium and stable isotopes of magmatic waters

To investigate the isotopic composition and age of water in volcanic gases and magmas, we analyzed samples from 11 active volcanoes ranging in composition from tholeiitic basalt to rhyolite: Mount St. Helens (USA), Kilauea (USA), Pacaya (Guatemala), Galeras (Colombia), Satsuma Iwo-Jima (Japan), Sierra Negra and Alcedo (Ecuador), Vulcano (Italy), Parícutin (Mexico), Kudryavy (Russia), and White Island (New Zealand). Tritium at relatively low levels (0.1–5 T.U.) is found in most emissions from high-temperature volcanic fumaroles sampled, even at discharge temperatures >700°C. Although magmatic fluids sampled from these emissions usually contain high CO₂, S_total, HCl, HF, B, Br, ³He R/R_A, and low contents of air components, stable isotope and tritium relations of nearly all such fluids show mixing of magmatic volatiles with relatively young meteoric water (model ages≤75 y). Linear δD/δ¹⁸O and ³H/δ¹⁸O mixing trends of these two end-members are invariably detected at arc volcanoes. Tritium is also detected in fumarole condensates at hot spot basalt volcanoes, but collecting samples approaching the composition of end-member magmatic fluid is exceedingly difficult. In situ production of ³H, mostly from spontaneous fission of ²³⁸U in magmas is calculated to be <0.001 T.U., except for the most evolved compositions (high U, Th, and Li and low H₂O contents). These values are below the detection limit of ³H by conventional analytical techniques (about 0.01 T.U. at best). We found no conclusive evidence that natural fusion in the Earth produces anomalous amounts of detectable ³H (>0.05 T.U.).     

Mantle source for Oldoinyo Lengai carbonatites: Evidence from helium isotopes in fumarole gases

Oldoinyo Lengai is the world's only active carbonatite volcano and considerable debate still surrounds the genesis of its magmas. Gases were collected from two fumaroles discharging close to the then active vent in October 2003. Measured fumarole temperatures were ≤ 195°C, despite the nearby, vigorous eruptive activity. Gases were sampled and analysed for noble gas isotopes. Freshly erupted natrocarbonatite lavas, a 1917 nephelinite and a sub-recent wollastonite bearing rock were also collected and analysed for noble gas isotopes using vacuum crushing techniques. In all the lava samples the neon, argon, krypton and xenon isotope ratio data are indistinguishable from air implying atmospheric contamination of the hygroscopic rocks. In the fumaroles, measured ³He/⁴He ratios are between 4 and 7 R/R_a. This range is similar to published values for silicate xenoliths of the East African Rift implying a local lithospheric mantle source for the volatile component of the Lengai magmas. It is still unclear if the natrocarbonatites themselves come from this region, or if fractionation and/or liquid immiscibility generate the carbonate magmas from a silicate melt within the crust itself.     

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

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

Helium isotopes and mantle volatiles in Loihi Seamount and Hawaiian Island basalts and xenoliths

We examine in this paper the use of helium isotope ratios for the study of hotspot volcanism along age-progressive island volcanic chains. The Hawaiian Islands are the original “high ³He” hotspot, with ³He/⁴He ratios as high as 32 × the atmospheric ratio; in the Pacific they stand out against the surrounding sea of MORB (rather uniformly 8 × atmospheric) which fills the entire Pacific with the exception of the Macdonald-Mehetia-Samoa axis in the South Pacific. The recent availability of a variety of alkalic and tholeiitic glasses from the U.S. Geological Survey and our own dredge hauls has prompted us to look first at isotopic variability within a single fresh and new volcano which is probably sitting directly atop a mantle plume. Thus we have looked in some detail at the total helium in glass pillow rims, at He in the enclosed vesicles, and at He in the glass itself, in both tholeiitic and alkalic lavas, and also at helium in associated phenocrysts and xenoliths. The measured ³He/⁴He ratios range from atmospheric to 30 × atmospheric, but we see clear evidence that the highly vesiculated lavas suffer exchange of He between the thin glass walls of vesicles and ambient seawater, so that we observe a post-eruptive isotopic disequilibrium between glass and gas phases. The primary effect is the very large loss of initial He content during eruptive vesiculation, which results in quite large isotopic effects from small additions of ambient He (of the order of 0.02 μcc He per gram of basalt; corresponding to a “water/rock ratio” of 0.5). Phenocrystic He in olivines verifies that the gas-phase He is not affected by vesicularities up to about 5%. Alkali basalt He appears to be independent of vesicularity up to values as high as 35%; this He is somewhat lower in ³He/⁴He ratio, but matches precisely the associated xenolithic He. However, from the present data we cannot exclude the possibility that diffusive exchange with seawater has affected the He ratio in alkalic vesicles.On the large scale, along the 10% of the Hawaiian chain available for subaerial sampling, we find high ³He/⁴He ratios (24 × atmospheric) in 5.5 × 10⁶-year-old lavas on Kauai. Maximum values of the ratio so far observed are in the pre-erosional Kula basalts on Maui, confirming the previous results of Kaneoka and Takaoka. Hawaii, where these high values were first observed is now seen to range from MORB ratios at Mauna Loa to only 15 × R_A at Kilauea fumaroles. Most xenolithic He so far measured is MORB He, but Loihi xenoliths have high values and are quite different in this respect. Finally, we discuss also the hydrogen and carbon isotope results on Loihi lavas, and show that these elements resemble MORB and appear not to show a distinctive plume signature.     

Chemical and isotopic compositions of thermal springs,fumaroles and bubbling gases at Tacaná Volcano (Mexico–Guatemala): implications for volcanic surveillance

This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO₃–SO₄ waters are thought to have formed by the absorption of a H₂S/SO₂–CO₂-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO₃-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ¹⁸O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at ~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ¹⁸O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO₂-dominated. The δ¹³C_CO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in ³He/⁴He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric ³He/⁴He ratio (R _A)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (⁴He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO₂/³He ratio of gases: bubbling springs with lower gas/water ratios show higher ³He/⁴He ratios and consequently lower CO₂/³He ratios (e.g. Zarco spring). Typical Central American CO₂/³He and ³He/⁴He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 10¹⁰ and 6.0 ± 0.9 R _A, respectively). The L/S (5.9 ± 0.5) and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc, Tacaná.     

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.     

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.     

Fumaroles in ice caves on the summit of Mount Rainier—preliminary stable isotope, gas, and geochemical studies

The edifice of Mount Rainier, an active stratovolcano, has episodically collapsed leading to major debris flows. The largest debris flows are related to argillically altered rock which leave areas of the edifice prone to failure. The argillic alteration results from the neutralization of acidic magmatic gases that condense in a meteoric water hydrothermal system fed by the melting of a thick mantle of glacial ice. Two craters atop a 2000-year-old cone on the summit of the volcano contain the world's largest volcanic ice-cave system. In the spring of 1997 two active fumaroles (T=62°C) in the caves were sampled for stable isotopic, gas, and geochemical studies.Stable isotope data on fumarole condensates show significant excess deuterium with calculated δD and δ¹⁸O values (−234 and −33.2‰, respectively) for the vapor that are consistent with an origin as secondary steam from a shallow water table which has been heated by underlying magmatic–hydrothermal steam. Between 1982 and 1997, δD of the fumarole vapor may have decreased by 30‰.The compositions of fumarole gases vary in time and space but typically consist of air components slightly modified by their solubilities in water and additions of CO₂ and CH₄. The elevated CO₂ contents (δ¹³C_CO2=−11.8±0.7‰), with spikes of over 10,000 ppm, require the episodic addition of magmatic components into the underlying hydrothermal system. Although only traces of H₂S were detected in the fumaroles, most notably in a sample which had an air δ¹³C_CO2 signature (−8.8‰), incrustations around a dormant vent containing small amounts of acid sulfate minerals (natroalunite, minamiite, and woodhouseite) indicate higher H₂S (or possibly SO₂) concentrations in past fumarolic gases.Condensate samples from fumaroles are very dilute, slightly acidic, and enriched in elements observed in the much higher temperature fumaroles at Mount St. Helens (K and Na up to the ppm level; metals such as Al, Pb, Zn Fe and Mn up to the ppb level and volatiles such as Cl, S, and F up to the ppb level).The data indicate that the hydrothermal system in the edifice at Mount Rainier consists of meteoric water reservoirs, which receive gas and steam from an underlying magmatic system. At present the magmatic system is largely flooded by the meteoric water system. However, magmatic components have episodically vented at the surface as witnessed by the mineralogy of incrustations around inactive vents and gas compositions in the active fumaroles. The composition of fumarole gases during magmatic degassing is distinct and, if sustained, could be lethal. The extent to which hydrothermal alteration is currently occurring at depth, and its possible influence on future edifice collapse, may be determined with the aid of on site analyses of fumarole gases and seismic monitoring in the ice caves.     

Sulfur isotopic effects in the disproportionation reaction of sulfur dioxide in hydrothermal fluids: implications for the δS variations of dissolved bisulfate and elemental sulfur from active crater lakes

Sulfur isotope effects during the SO₂ disproportionation reaction to form elemental sulfur (3SO₂+3H₂O→2HSO₄⁻+S+2H⁺) at 200–330°C and saturated water vapor pressures were experimentally determined. Initially, a large kinetic isotopic fractionation takes place between HSO₄⁻ and S, followed by a slow approach to equilibrium. The equilibrium fractionation factors, estimated from the longest run results, are expressed by 1000 ln α_HSO4⁻–S=6.21×10⁶/T²+3.62. The rates at which the initial kinetic fractionation factors approach the equilibrium ones were evaluated at the experimental conditions.δ³⁴S values of HSO₄⁻ and elemental sulfur were examined for active crater lakes including Noboribetsu and Niseko, (Hokkaido, Japan), Khloridnoe, Bannoe and Maly Semiachik (Kamchatka), Poás (Costa Rica), Ruapehu (New Zealand) and Kawah Ijen and Keli Mutu (Indonesia). Δ_HSO4⁻–S values are 28‰ for Keli Mutu, 26‰ for Kawah Ijen, 24‰ for Ruapehu, 23‰ for Poás, 22‰ for Maly Semiachik, 21‰ for Yugama, 13‰ for Bannoe, 9‰ for Niseko, 4‰ for Khloridonoe, and 0‰ for Noboribetsu, in the decreasing order. The SO₂ disproportionation reaction in the magmatic hydrothermal system below crater lakes where magmatic gases condense is responsible for high Δ_HSO4⁻–S values, whereas contribution of HSO₄⁻ produced through bacterial oxidation of reduced sulfur becomes progressively dominant for lakes with lower Δ_HSO4⁻–S values. Currently, Noboribetsu crater lake contains no HSO₄⁻ of magmatic origin. A 40-year period observation of δ³⁴S_HSO4⁻ and δ³⁴S_S values at Yugama indicated that the isotopic variations reflect changes in the supply rate of SO₂ to the magmatic hydrothermal system. This implies a possibility of volcano monitoring by continuous observation of δ³⁴S_HSO4⁻ values. The δ¹⁸O values of HSO₄⁻ and lake water from the studied lakes covary, indicating oxygen isotopic equilibration between them. The covariance gives strong evidence that lake water circulates through the sublimnic zone at temperatures of 140±30°C.     

CO<Subscript>2</Subscript> and He degassing at El Chichón volcano,Chiapas, Mexico: gas flux,origin and relationship with local and regional tectonics

During 2007–2008, three CO₂ flux surveys were performed on El Chichón volcanic lake, Chiapas, Mexico, with an additional survey in April 2008 covering the entire crater floor (including the lake). The mean CO₂ flux calculated by sequential Gaussian simulation from the lake was 1,190 (March 2007), 730 (December 2007) and 1,134 g m⁻² day⁻¹ (April 2008) with total emission rates of 164 ± 9.5 (March 2007), 59 ± 2.5 (December 2007) and 109 ± 6.6 t day⁻¹ (April 2008). The mean CO₂ flux estimated from the entire crater floor area was 1,102 g m⁻² day⁻¹ for April 2008 with a total emission rate of 144 ± 5.9 t day⁻¹. Significant change in CO₂ flux was not detected during the period of survey, and the mapping of the CO₂ flux highlighted lineaments reflecting the main local and regional tectonic patterns. The ³He/⁴He ratio (as high as 8.1 R _A) for gases in the El Chichón crater is generally higher than those observed at the neighbouring Transmexican Volcanic Belt and the Central American Volcanic Arc. The CO₂/³He ratios for the high ³He/⁴He gases tend to have the MORB-like values (1.41 × 10⁹), and the CO₂/³He ratios for the lower ³He/⁴He gases fall within the range for the arc-type gases. The high ³He/⁴He ratios, the MORB-like CO₂/³He ratios for the high ³He/⁴He gases and high proportion of MORB-CO₂ (M = 25 ±15%) at El Chichón indicate a greater depth for the generation of magma when compared to typical arc volcanoes.     

The determination of deep temperatures by means of the CO-CO2-H2-H2O geothermometer: an example using fumaroles in the Campi Flegrei,Italy

Chromatographic analyses of fumarolic gases, collected in sampling bottles containing an alkaline solution, have been carried out using a thermal conductivity detector and a flame ionization detector, after catalytic conversion of CO and CH₄. The latter method enables the concentration of carbon monoxide to be measured with sufficient accuracy for use in a CO-CO₂-H₂-H₂O geothermometer. Application of this geothermometer to fumaroles in the crater of Solfatara in the Campi Flegrei, Italy, indicates that they are fed from a steam reservoir at 250±15 °C and at 10^–36±2atm of oxygen. On the other hand, the CH₄-CO₂-H₂-H₂O geothermobarometer seems to re-equilibrate at superficial temperatures and cannot be used for infering thermodynamic conditions at depth. Regular sampling of these fumaroles together with a geothermometric interpretation of the gas analyses provides a means of monitoring, with comparative accuracy, the chemical and thermal evolution of the hydrothermal reservoir below the Solfatara crater. Such monitoring would probably detect an increase in temperature at depth and the injection of magmatic gas into the reservoir.     

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.