Oxygen and hydrogen isotopes in the volcano-sedimentary complex of Huelva (Iberian Pyrite Belt): example of water circulation through a volcano-sedimentary sequence

The minerals of basic and acidic rocks from the volcano-sedimentary sequence in the Huelva area, Spain, Iberian Pyrite Belt, display an extendedδ¹⁸O enrichment. Quartzδ¹⁸O values from quartz-keratophyres vary from +10.5 to +17.0 and feldsparδ¹⁸O values from +14.4 to +16.0. For the spilite or spilitized doleritesδ¹⁸O values vary from +9.9 to +13.4 for feldspar, from +6.4 to +9.8 for chlorite, from +3.7 to +4.3 for ilmenite and from +13.6 to +14.0 for quartz, but pyroxene exhibits magmatic values, from +5.3 to +6.1 with an exception at +7.5. The chloriteδD values vary from −34 to −43‰.This is attributed to hydrothermal alteration with seawater enriched inδ¹⁸O by circulation through sediments.The temperatures of interaction determined from isotopic fractionations between minerals range from 400° to 520°C.CalculatedδD andδ¹⁸O values for water in equilibrium with the minerals at isotopic temperatures range from −16 to +5 and from +8.3 to +12.8, respectively.A model of circulation of seawater through a pile of sedimentary rocks and then through basaltic rocks is proposed to explain the high¹⁸O compositions of the rocks from the Huelva District. Water/rock mass ratios calculated from this model range between 0.3 and 0.7 for the determined range of temperatures.     

Water–Rock interactions in the basement beneath Long Valley Caldera: an oxygen isotope study of the Long Valley Exploratory Well drill cores

The Long Valley Exploratory Well, at the center of the Resurgent Dome of Long Valley caldera, penetrated pre-caldera basement rocks at a depth of 2101.72–2313.0 m, beneath the caldera-forming Bishop Tuff and post-caldera Early Rhyolite. The basement rocks contain prominent quartzites, with ubiquitous milky white quartz veins (with minor calcite and pyrite) and fractures of varied orientation and geometry. The other members of the basement sequence are very fine-grained quartz-rich graphitic pelites with calcite veins, spotted hornfels, and shallow intrusive rocks. Previous studies established the presence of a post-caldera, paleohydrothermal system (500–100 ka) to a depth of 2000 m that affected the Bishop Tuff and a recent (40 ka to present) hydrothermal system at shallow depth (<1 km). The deeper extent of these hydrothermal activities is established in this paper by a detailed oxygen isotope analysis of the drill core samples. 238 analyses of δ¹⁸O in 50 quartz veins within the 163.57 m depth interval of basement rocks reveal extreme heterogeneity in δ¹⁸O values (8–19.5‰). Majorities of the 84 bulk analyses of quartzites show variation of δ¹⁸O within a narrow range of 14–16‰. However, certain samples of these quartzites near the contacts with veins and fractures exhibit sharp drops in δ¹⁸O. The interbedded pelitic rocks and spotted hornfels have whole-rock δ¹⁸O ranging from 2.2 to 11.8‰. Clear, euhedral vuggy quartz that partially fills earlier open fractures in both the quartzites and quartz veins, has distinctive δ¹⁸O, ranging between −3.2 and +8.4‰. Low values of δ¹⁸O are also found in the hydrothermal minerals and whole rocks adjacent to the thin veins, clearly indicating infiltration of meteoric water. Three distinct observed patterns of fractionation in δ¹⁸O between veins and host quartzites are analyzed with the principles of mass balance, equilibrium oxygen isotope fractionation in closed system, and kinetically controlled oxygen isotope exchange in an open system. This analysis suggests that the early quartz veins formed due to a magmatic-hydrothermal activity with no influx of external water once the system comprising the sedimentary envelope and a magmatic-hydrothermal fluid phase became closed. Two-stage isotopic exchange processes caused fractionation in the δ values that originally formed arrays with slope 1 in a δ_{vein quartz}–δ_{host quartzite} space. Another array in the same space, with near zero slope was also formed due to variation in temperature, initial isotopic compositions of the quartzite sequence and the fluid phase. Variation in temperature was mostly in the range of 300–400°C giving Δ (=δ_{vein quartz}–δ_{host quartzite})≈−2.8 to +2.8. The δ¹⁸O of the fluid could range from −5 to +10; however a narrower range of +5 to +10 can explain the data. This episode of hydrothermal activity could take place either as a single pulse or in multiple pulses but each as a closed system. A later, fracture-controlled, meteoric water (δ¹⁸O−0.46 to −12.13) flow and interaction (at 250°C) is interpreted from the analysis of δ¹⁸O values of the coexisting quartz and calcite pairs and existence of markedly ¹⁸O-depleted pelitic horizons interbedded with ¹⁸O-enriched quartzite layers. Thus, the interpreted earlier magmatic-hydrothermal activity was overprinted by a later meteoric-hydrothermal activity that resulted in steep arrays of δ¹⁸O values in the δ_{vein quartz}–δ_{host quartzite} space. Calculations show that the likely life span of the post-caldera, hydrothermal activity in the depth range of 2.1–2.3 km beneath Long Valley was 0.08–0.12 Ma. Diffusive ±advective transport of oxygen isotopes from fracture-channelized meteoric water to nearly impermeable wall rocks caused a lowering of δ¹⁸O values in the quartz over short distances and in calcites over greater distances. Thus, the hydrothermal activity appears pervasive even though the meteoric water flow was primarily controlled by fractures.     

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.     

Geothermal assessment of the island of ischia (southern Italy) from isotopic and chemical composition of the delivered fluids

The Ischia geothermal system is hosted by silicic rocks of the Quaternary Potassic Roman Province, in southern Italy. Exploration drilling down to 1156 m depth in the mid-1950s provided information on boiling profiles (up to 250°C) and on the depth and permeability of the potential reservoirs. Discharge fluid samples were collected and analyzed to define the inflow of surrounding seawater (C1 ranges from 2.5 to 20 g/kg) into the system.Analyses of samples from surface manifestations and shallow wells collected during 1983 and 1988 point to the existence of three distinct mixing regimes, involving three water components. A dishomogeneous body of diluted water (Cl less than 2.5 g/kg), that occurs at depths > 700 m and reequilibrates at 240°C at least, is overlain by an aquifer of groundwater variably mixed with variably seawater (Cl from 4 to 10 g/kg), which tends to reequilibrate at 160°C. Steam-heated waters locally develop and act as dilutants of the rising geothermal fluids.Dilution, mixing, and evaporation of the ascending chloride fluids are supported by oxygen and hydrogen isotopic data the thermal waters being enriched in ¹⁸O and D with respect to local meteoric water by up to 7 and 30‰, respectively. The relative composition of the major cations in thermal solutions was used to discriminate the two main groups of thermal waters, the reservoir temperatures of which are estimated from the Na/K-gethermometer. K-Mg geothermometer indicates reequilibration in near-surface conditions.The isotopic composition of the fumarolic steam varies from −7 to −12‰ in ∂⁸O and from − 35 to − 70‰ in ∂D, in agreement with a deep mixed fluid that boils adiabatically from 240 to 80°C. The deuterium content of the H₂O-H₂ pair gives enrichment factor of about 830‰, corresponding to equilibrium temperature conditions slightly higher than the surface boiling temperatures. The ∂¹³C of CO₂is almost constant at −4.5‰ (1δ=0.4), suggesting an important magmatic contribution, and the ∂¹⁸O values of CO₂appears to in equilibrium with accompanying steam at the measured temperatures.The CO₂/Ar and H₂/Ar chemical ratios have been used to derive aquifer temperatures, the values obtained being consistent with those of solute geothermometers.     

S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

Hydrothermal vent waters at 13°N on the East Pacific Rise: isotopic composition and gas concentration

Gas concentrations and isotopic compositions of water have been measured in hydrothermal waters from 13°N on the East Pacific Rise. In the most Mg-depleted samples ( 5 × 10⁻³ moles/kg) the gas concentrations are: 3–4.5 × 10⁻⁵ cm³ STP/kg helium, 0.62–1.24 cm³ STP/kg CH₄, 10.80–16.71 × 10⁻³ moles/kg CO₂. The samples contain large quantities (95–126 cm³/kg) of H₂ and some carbon monoxide (0.26–0.36 cm³/kg) which result from reaction with the titanium sampling bottles. δ¹³C in methane and CO₂ (−16.6 to −19.5 and −4.1 to −5.5 respectively) indicate temperatures between 475 and 550°C, whereas δ¹³C_CO is compatible with formation by reduction of CO₂ on Ti at 350°C close to the sampling temperature.³He/⁴He are very homogeneous at (7.5 ± 0.1)R_A(³He/⁴He = 1.0 × 10⁻⁵) and very similar to already published data as well as CH₄/³He ratios between 1.4 and 2.1 × 10⁶.¹⁸O and D in water show enrichments from 0.39 to 0.69‰ and from 0.62 to 1.49‰ respectively. These values correspond to W/R ratios of 0.4–7. The distinct¹⁸O enrichments indicate that the isotopic composition of the oceans is not completely buffered by the hydrothermal circulations. The³He-enthalpy relationship is discussed in terms of both hydrothermal heat flux and³He mantle flux.     

Authigenic carbonates in sediments from the Gulf of Mexico

The carbon isotopic composition of diagenetic dolomite and calcite in some sediments of the Gulf of Mexico varies between “normal-marine” (δ¹³C ca. 0‰) and −14.6‰ which suggests that biogenic CO₂ contributed to the carbonate formation. The δ¹³O values of dolomite and coexisting calcite are very similar but variable down-core.Dolomite and calcite precipitated early from pore water where SO₄²⁻ was not reduced. However, during (and after?) SO₄²⁻ reduction dolomite and calcite still formed and there are at least two generations of carbonate minerals present.     

Origin of waters responsible for serpentinization of the Izu-Ogasawara-Mariana forearc seamounts in view of hydrogen and oxygen isotope ratios

Many serpentinite seamounts occur over a region 20–120 km west of the trench axis in the Izu-Ogasawara-Mariana forearc regions. The hydrogen and oxygen isotopic compositions of serpentine from these regions indicate that there are at least two kinds of waters responsible for serpentinization: seawater and water derived from dehydration of the descending slab. Serpentine from two Mariana and two Torishima samples with microscopically ductile and sheared texture (sheared-type) have lowerδD(−63to−52‰) and slightly higherδ18O values (+6.1 to +8.2‰) than that of other nine Ogasawara samples with mesh texture (mesh-type) (δD= −43to−49‰ andδ¹⁸O= +5.8to+6.7‰). This suggests that the sheared-type serpentine with lowerδD and slightly higherδ¹⁸O values was formed within the wedge mantle by interaction with water derived from a descending slab. The sheared texture is likely to have been produced during diapiric uplift. The unaltered portion of the ultramafic bodies later interacted with seawater after emplacement at or near the seafloor, resulting in formation of the mesh-type serpentine with higherδD values.     

Low-temperature opal-CT precipitation in Antarctic deep-sea sediments: evidence from oxygen isotopes

Porcellanite has been found in Antarctic deep-sea sediments of shallow burial depth at four different sites in host sediments younger than 4 Ma. Oxygen isotope analysis shows that the opal-CT samples are extremely rich in¹⁸O (δ¹⁸O= 41.2to44.7‰ rel. SMOW). According to the quartz/water fractionation the calculated isotopic opal-CT formation temperature is in the range of 0 to 4°C. This agrees well with sediment temperature measurements. The low opal-CT precipitation temperature contrasts with current ideas about later diagenetic formation of opal-CT at higher temperatures of 18 to 56°C.     

Chemical and stable isotopic models for boundary creek warm springs, southwestern Yellowstone National Park, Wyoming

Thermal springs of the Boundary Creek hydrothermal system in the southwestern part of Yellowstone Park outside the caldera boundary vary in chemical and isotopic composition, and temperature. The diversity may be accounted for by a combination of processes including boiling of a deep thermal water, mixing of the deep thermal water with cool meteoric water and/or with condensed steam or steam-heated meteoric water, and chemical reactions with surrounding rocks. Dissolved-silica, Na⁺, K⁺ and Ca²⁺ contents of the thermal springs could result from a thermal fluid with a temperature of 200 ± 20°C. Chloride-enthalpy and silica-enthalpy mixing models suggest mixing of 230°C, 220 mg/l Cl⁻ thermal water with cool, low-Cl⁻ components. A 350 to 390°C component with Cl⁻ ≥ 300 mg/l is possibly present in thermal springs inside the caldera but is not required to fit observed spring chemical and isotopic compositions. Irreversible mass transfer models in which a low-temperature water reacts with volcanic glass as it percolates downward and warms, can account for observed pH and dissolved-silica, K⁺, Na⁺, Ca²⁺ and Mg²⁺ concentrations, but produces insufficient Cl⁻ or F⁻ for measured concentrations in the warm springs. The ratio of a_Na/a_H, and Cl⁻ are best accounted for in mixing models. The water-rock interaction model fits compositions of acid-sulfate waters observed at Summit Lake and of low-Cl⁻ waters involved in mixing.The cold waters collected from southwestern Yellowstone Park have δD values ranging from −118 to −145 per mil and δ¹⁸O values of −15.9 to −19.4 per mil. Two samples from nearby Island Park have δD values of −112 and −114 per mil and δ¹⁸O values of −15.1 and −15.3 per mil. All samples of thermal water plot significantly to the right of the meteoric water line. The low Cl⁻ and variable δD values of the thermal waters indicate isotopic compositions are derived by extensive dilution with cold meteoric water and by steam separation on ascent to the surface. Many of the hot springs with higher δD values may contain in addition a significant amount of high-D, low-Cl⁻, acid-sulfate or steam-heated meteoric water. Mixing models, Cl⁻ content and isotopic compositions of thermal springs suggest that 30% or less of a deep thermal component is present. For example, the highest-temperature springs from Three Rivers, Silver Scarf and Upper Boundary Creek thermal areas contain up to 70% cool meteoric water and 30% hot water components, springs at Summit Lake and Middle Boundary Creek spring 57 are acid-sulfate or steam-heated meteoric water; springs 27 and 48 from Middle Boundary Creek and 49 from Mountain Ash contain in excess of 50% acid-sulfate water; and Three Rivers spring 46 and Phillips could result from mixing hot water with 55% cool meteoric water followed by mixing of acid-sulfate water. Extensive dilution by cool meteoric water increases the uncertainties in quantity and nature of the deep meteoric, thermal component.     

Earthquake-induced variations in the composition of the water in the geothermal reservoir at Vulcano Island, Italy

During 1979–1989, variations were observed in the oxygen composition of the water contained in the geothermal reservoir at Vulcano Island, Italy.The reservoir water, that has a magmatic origin, showed an oxygen composition of +1.0±0.5‰ δ¹⁸O during periods without local tectonic earthquakes, and an oxygen composition of +3.4±0.5‰ δ¹⁸O after the highest-energy seismic activity that occurred recently near the island. A slight increase of the δ¹⁸O value in the reservoir water was also observed after a low-energy sequence of tectonic earthquakes that occurred at very shallow depth just beneath Vulcano Island. These ¹⁸O variations in the reservoir water are consistent with earthquake-induced increases in the contribution from high-temperature δ¹⁸O-rich magmatic condensate to the geothermal reservoir, and with subsequent decreases in the δ¹⁸O value due to ¹⁸O exchanges at the temporarily increased reservoir temperature during reactions between the highly reactive magmatic condensate and the local rocks.Only minor changes in the deuterium composition of the reservoir water occurred with time, as the δD value in the magmatic condensate released from the magma after major local earthquakes quickly approached the δD value of the water contained in the geothermal reservoir.Also the chloride concentration in the reservoir water appears to be linked to the contribution from the magmatic fluid. This chloride content seems not to have undergone major changes with time, as it may be buffered by temporary increases in the reservoir temperature up to values >300°C induced by major local earthquakes. This mechanism may possibly occur also in other magmatic–hydrothermal systems.     

Oxygen isotope evidence for past and present hydrothermal regimes of Long Valley caldera, California

Whole-rock oxygen isotope compositions of cores and cuttings from Long Valley exploration wells show that the Bishop Tuff has been an important reservoir for both fossil and active geothermal systems within the caldera. The deep Clay Pit-1 and Mammoth-1 wells on the resurgent dome penetrate mildly to strongly altered Bishop Tuff with δ¹⁸O_WR values as low as −2.6% (vs V-SMOW). The idfu 44-16 well intercepts a thinner Bishop Tuff section with δ¹⁸O_WR values of +0.4 to +2.3%. in the western caldera moat, where milder and more sporadic ¹⁸O depletions occur in Tertiary volcanic rocks of the western caldera floor (δ¹⁸O_WR = +2.2 to +6.4‰). Bishop Tuff samples from deeper parts of the 715 m rdo-8 (Shady Rest) well in the SW moat are also strongly depleted in ¹⁸O (δ¹⁸O_WR = −1.5 to +0.6‰). Four shallow thermal gradient wells (469–715 m td drilled in the western moat did not penetrate Bishop Tuff, but Early Rhyolites from two of these holes are depleted in ¹⁸O (δ¹⁸O_WR = −1.2 to +6.0‰ inplv-1 +4.6 to +5.3%. inmlgrap-1), compared to lithologic equivalents from the other two holes (δ¹⁸O_WR = +6.3 to +8.0‰ inplv-2 andmlgrap-2).Whole-rock oxygen isotope profiles for the resurgent dome wells are unlike profiles calculated assuming alkali feldspar-H₂O fractionation behavior and total O-isotopic equilibration with −14.3‰ fluids at measured temperatures. The sense of this divergence implies an earlier hydrothermal episode within the central caldera driven by one or more shallow intrusions. Geochemical similarities between an intrusive granophyre at the bottom of the Clay Pit-1 well and a nearby Moat Rhyolite dome with a K/Ar cooling age of 0.5 Ma suggest that vigorous hydrothermal activity beneath the central resurgent dome may have occurred as much as 0.5 m.y. ago. Calculated and measured O-isotope profiles are similar for deep wells that penetrate the western moat of the caldera, where steep temperature gradients and low δ¹⁸O_WR values in Early Rhyolites from plv-1 are attributed to an active hydrothermal aquifer that has descended slightly from earlier, shallower elevations. Similarly, severe ¹⁸O depletions in Bishop Tuff samples from the idfu 44-16 and rdo-8 wells reflect active convection beneath the western moat, whereas milder ¹⁸O depletions in Early Rhyolites from mlgrap-1 were apparently caused by hydrothermal alteration at lower temperatures. The O-isotope profiles imply that surface discharge within and around the resurgent dome results from shallow, eastward-directed outflow from a zone of higher enthalpy hydrothermal upflow beneath the western caldera moat. Intrusive magmatic heat source(s) are inferred to exist beneath the western moat, perhaps beneath Mammoth Mountain.     

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.     

Stable isotope compositions and water contents of boninite series volcanic rocks from Chichi-jima, Bonin Islands, Japan

Measurements of stable isotope compositions and water contents of boninite series volcanic rocks from the island of Chichi-jima, Bonin Islands, Japan, confirm that a large amount (1.6–2.4 wt.%) of primary water was present in these unusual magmas. An enrichment of 0.6‰ in¹⁸O during differentiation is explained by crystallization of¹⁸O-depleted mafic phases. Silicic glasses have elevated δ¹⁸O values and relatively low δD values indicating that they were modified by low-temperature alteration and hydration processes. Mafic glasses, on the other hand, have for the most part retained their primary isotopic signatures since Eocene time. Primary δD values of −53 for boninite glasses are higher than those of MORB and suggest that the water was derived from subducted oceanic lithosphere.     

An oxygen isotope study of hydrothermal alteration in the Lake City caldera, San Juan Mountains, Colorado

A 23-m.y.-old, fossil meteoric-hydrothermal system in the Lake City caldera (11 × 14 km) has been mapped out by measuring δ ¹⁸O values of 300 rock and mineral samples. δ ¹⁸O varies systematically throughout the caldera, reaching values as low as −2. Great topographic relief, regional tilting, and variable degrees of erosion within the caldera all combine to give us a very complete section through the hydrothermal system, from the surface down to a depth of more than 2000 m. The initial δ ¹⁸O value of the caldera-fill Sunshine Peak Tuff was very uniform (+7.2 ± 0.1), making it easy to determine the exact amount of ¹⁸O depletion experienced by each sample during hydrothermal alteration. Also, we have excellent stratigraphic control on depths beneath the mid-Tertiary surface, quantitative information on mineralogical alteration products, and accurate data on the shape of the central resurgent intrusion, which was the principal ‘heat engine’ that drove the hydrothermal circulation. Major conclusions are: (1) Although pristine mid-Tertiary meteoric waters in this area had δ ¹⁸O −14, these fluids were ¹⁸O-shifted upward to about δ¹⁸O = −8 to −5 prior to entering the shallow convective system associated with the resurgent intrusive rocks. Although there was undoubtedly radial inflow toward the caldera from all directions, the highly fractured Eureka Graben, southwest of the caldera, was probably the principal source of recharge groundwater for the Lake City system. (2) Fluid flow within the caldera was dominated by three major categories of permeable zones: the porous megabreccia units (which dip outward from the resurgent dome), vertical fractures and faults related to resurgence, and the caldera ring fault itself. All of these zones exhibit marked ¹⁸O depletions, and they are also typically intensely mineralogically altered. (3) The resurgent intrusive stock and its contact metamorphic aureole of hornfels both experienced water/rock ratios lower than the permeable zones; however, they have similarly low δ ¹⁸O values because they were altered at higher temperatures. (4) Throughout the caldera, the δ ¹⁸O of Sunshine Peak Tuff decreases with increasing depth (about 6 per mil/km), indicative of a shallow thermal gradient, typical of a convective hydrothermal system. The near-surface portion of this gradient was controlled by the temperature drop associated with boiling in the uprising fluid. (5) Deeply circulating meteoric water rose along permeable ring fractures 3 to 5 km beneath the mid-Tertiary surface. These fluids were drawn into the shallow convective system through the lower, porous, megabreccia units. Near the resurgent intrusions, fluid flow was again directed upward where resurgence-related, near-vertical fractures intersect the megabreccia units.     

Nitrogen isotope geochemistry of basaltic glasses: implications for mantle degassing and structure?

The nitrogen isotope geochemistry of 15 basaltic glasses has been investigated using stepped heating and high sensitivity static vacuum mass spectrometry. At low temperature (< 600°C) the glasses release small amounts of nitrogen with δ¹⁵N_AIR, averaging −0.3‰, suggesting surficial adsorption of atmospheric nitrogen. At high temperature, usually with a maximum at 1000°C, indigenous nitrogen with a concentration ranging from 0.2 to 2.1 ppm is released. The δ¹⁵N values of this high temperature release show a wide range from −4.5‰ to +15.5‰. There is no correlation between N ppm and δ¹⁵N, and the samples apparently form 3 groups with distinctive δ¹⁵N. Six MORB glasses from the Mid-Atlantic Ridge, East Pacific Rise and Juan de Fuca Ridge define a group with δ¹⁵N = +7.5 ± 1.3‰. In contrast two Indian Ocean MORB glasses (Carlsberg Ridge and Gulf of Aden) gave negative δ¹⁵N averaging −3.2‰. Glasses from Loihi Seamount have high δ¹⁵N averaging +14.0 ± 1.0‰. Comparison of the δ¹⁵N data with the mantle models derived from helium and argon isotope studies suggests that the wide range in δ¹⁵N may reflect in part heterogeneities in the mantle related to its degassing history. It is possible, however, that magmatic degassing processes have also affected nitrogen isotopic compositions, and the data cannot yet be unambiguously interpreted in terms of source variations.     

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 signatures of the basement rocks from the Campi Flegrei geothermal field (Naples, southern Italy): inferences about the origin and evolution of its hydrothermal fluids

The Campi Flegrei (Naples, Campanian Plain, southern Italy) geothermal system is hosted by Quaternary volcanic rocks erupted before, during and after the formation of the caldera that represents one of the major structural features in the Neapolitan area. The volcanic products rest on a Mesozoic carbonate basement, cropping out north, east and south of the area. Chemical (major, minor and trace elements) and stable isotope (C, H, O) analyses were conducted on drill-core samples recovered from geothermal wells MF-1, MF-5, SV-1 and SV-3, at depths of ˜ 1100 to 2900 m. The study was complemented by petrographic and SEM examination of thin sections. The water which feeds the system is both marine and meteoric in origin. Mineral zonation typical of a high-temperature geothermal system exists in all the geothermal wells; measured temperatures in wells are as high as ˜ 400 °C. The chemical composition of the waters suggests the existence of two reservoirs: a shallow reservoir (depth < 2000 m) fed by seawater that boiled at 320 °C and became progressively diluted by steam-heated local meteoric water during its ascent; and a deeper reservoir (depth > 2000 m) of hypersaline water. The drill-cores are mainly hydrothermally altered volcanics of trachy-latitic affinity, but some altered pelites and limestones are also present. Published Na, Mg and K concentrations of selected geothermal waters indicate that the hydrothermal fluids are in equilibrium with their host rocks, with respect to K-feldspar, albite, sericite and chlorite. The measured δ¹⁸O_(SMOW) values of rocks range from +4.3 to + 16.5%. The measured δD_(SMOW) values range from − 79 to − 46%. The calculated isotopic composition of the fluids at equilibrium with the samples vary from + 1 to + 8.3%. δ¹⁸O and from − 52 to + 1%. δD. The estimated isotopic composition of the waters at equilibrium with the studied samples confirmed the existence of two distinct fluid types circulating in the geothermal system. The shallower has a marine water signature, while the deeper water has a signature consistent both with magmatic and meteoric origins. In the latter case, the recharge of this aquifer likely occurs at the outcrop of the Mesozoic Limestones surrounding the Campanian Plain; after infiltration, the water percolates through evaporitic layers, becoming hypersaline and D-depleted.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Strontium stable isotopes fractionate in the soil environments?

This study shows that the stable isotopic composition of strontium (the ⁸⁸Sr/⁸⁶Sr ratio expressed as δ^88/86Sr value relative to the NBS987 standard) varies significantly in sedimentary terrestrial environments. The abundances of ⁸⁶Sr, ⁸⁸Sr isotopes were analyzed by MC-ICP-MS “Nu Plasma”. All studied rocks and waters show δ^88/86Sr values that are distinctly different from the measured NBS987 standard (yielding 0.01 ± 0.05‰, all errors are reported as 2σ). Modern corals from the northern Gulf of Aqaba, Red Sea yielded significantly different value than seawater (δ^88/86Sr = 0.22 ± 0.07‰, compared to 0.35 ± 0.06‰, respectively), in an excellent correlation with the δ^88/86Sr analyses reported by Fietzke and Eisenhauer [Fietzke, J., Eisenhauer, A., 2006. Determination of temperature-dependent stable strontium isotopes (⁸⁸Sr/⁸⁶Sr) fractionation via bracketing standard MC-ICP-MS. Geochm. Geophys. Geosyst. 7 (no. 8)] on other coral samples. All carbonate samples that originated in the marine environment: corals (porites and acropora from the northern Gulf of Aqaba); Cretaceous limestone and runoff from the Judea Mountains as well as lacustrine evaporitic aragonite (Dead Sea); and Red Sea and Atlantic seawater yield an average δ^88/86Sr value of 0.26 ± 0.1‰. On the other hand, secondary materials (products of chemical weathering) from the terrestrial environment of the Judea Mountain such as terra rossa soil and speleothem calcite (that derives its Sr from the above-lying soil) yielded significantly lower δ^88/86Sr value of − 0.17 ± 0.06‰. This indicates that strontium isotopes fractionate in the soil environment calling for a possible development of strontium isotopes as a tracer for processes of chemical weathering and pedogenesis.