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.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Oxygen isotopes in coexisting garnets, clinopyroxenes and phlogopites of Roberts Victor eclogites: implications for petrogenesis and mantle metasomatism

δ¹⁸O values of coexisting garnet, clinopyroxene and phlogopite for twelve compositionally and texturally diverse Roberts Victor eclogite xenoliths range from +3.8 to +7.1, +4.0 to +7.4 and +5.9 to +7.4, respectively. Differences between theδ¹⁸O values of coexisting garnets and clinopyroxenes are normally zero; however, there is some variation in theδ¹⁸O values of different fractions of the same mineral in four samples which suggests the presence of isotopic zonation and inhomogeneity, possibly resulting from the introduction of a secondary fluid which metasomatized the eclogites and resulted in the formation of phlogopite, amphibole and celsian. Theδ¹⁸O value of the metasomatic fluid is generally buffered by the isotopic composition of the primary garnet and clinopyroxene, as indicated by a correlation between the isotopic composition of phlogopite and the primary pyroxene and garnet.The large range inδ¹⁸O values of the eclogites and the similarity in the isotopic composition of coexisting pyroxene and garnet support the interpretation that the Roberts Victor eclogites represent metamorphosed, altered basalts. The eclogites were subjected to infiltration metasomatism in the mantle prior to their incorporation in the kimberlite, and the source of this fluid was probably unrelated to the eclogite.     

O/O mapping and hydrogeology of a short-lived (≈10 years) fumarolic (>500°C) meteoric–hydrothermal event in the upper part of the 0.76 Ma Bishop Tuff outflow sheet, California

¹⁸O/¹⁶O data from the 200-m-thick, 0.76 Ma Bishop Tuff outflow sheet provide evidence for a vigorous, short-lived (≈10 years), high-temperature, fumarolic meteoric–hydrothermal event. This is proved by: (1) the juxtaposition in the upper, partially welded Bishop Tuff of low-¹⁸O groundmass/glass (δ¹⁸O=−5 to +3) with coexisting quartz and feldspar phenocrysts having magmatic δ¹⁸O values (+8.7±0.3; +7.5±0.3); and (2) the fact that these kinds of ¹⁸O/¹⁶O signatures correlate very well with morphological features and mapped zones of fumarolic activity. Profiles of δ¹⁸O with depth in the Bishop Tuff within the fumarole area define a 40- to 50-m-thick, low-¹⁸O, stratigraphic zone that is sandwiched between the essentially unwelded near-surface portion of the tuff and an underlying, densely welded black tuff that displays magmatic ¹⁸O/¹⁶O values. Shallow-dipping columnar joints and other fumarolic features (i.e., subhorizontal tubular conduits and steep fissures) correlate very well with these pervasively devitrified, low-¹⁸O zones. The base of the low-¹⁸O zone is extremely sharp (3‰ per meter) and is located directly above the transition from partially welded tuff to densely welded black tuff. The observed average whole-rock ¹⁸O-depletions within this low-¹⁸O zone are about 6–7‰, requiring meteoric water/rock ratios in excess of 0.24 in mass units. Rainfall on the surface of the tuff would not have been high enough to supply this much H₂O in the short lifetime of fumarolic activity, suggesting that some recharge must have been from groundwater flow through the upper part of the tuff, above the sloping (1°–5°) top of the impermeable lower zone. This is compatible with the observation that the fumarolic areas roughly correlate with the preeruptive regional drainage pattern. Some of this recharge may in part have been from the lake that filled Long Valley caldera, which was dammed by the Bishop Tuff up to the level of this boundary between the partially and densely welded zones (≈7000 ft, the elevation of the highest Long Valley Lake shorelines). Gazis et al. had previously shown that the 2.8-Ma intracaldera Chegem Tuff from the Caucasus Mountains exhibits exactly the same kind of ¹⁸O-signature that we have correlated with fossil fumaroles in the Bishop Tuff outflow sheet. Although not recognized as such by McConnell et al.; ¹⁸O/¹⁶O data from drill-hole samples from the intracaldera Bishop Tuff in Long Valley also display this characteristic ¹⁸O signature (i.e., analogous δ¹⁸O-depth profiles, as well as low-¹⁸O groundmass coexisting with high-¹⁸O feldspar phenocrysts). This fumarolic ¹⁸O/¹⁶O signature is observed to much greater depths (≈650–750 m) in the intracaldera tuffs (≈1500 m thick) than it is in the ≈200-m-thick Bishop Tuff outflow sheet (≈80 m depth).     

O, S, Sr, and Pb isotope variations in volcanic rocks from the Northern Mariana Islands: implications for crustal recycling in intra-oceanic arcs

Quaternary lavas from the Northern Mariana Islands have respective O- and S-isotope ranges ofδ¹⁸O = +5.7 to +6.6 (‰ SMOW) andδ³⁴S = +2.0to+20.7 (‰ CDT). Chemically evolved andesites and dacites with meanδ¹⁸O = +6.3 ± 0.2 are slightly enriched in¹⁸O with respect to unfractionated basalts of<53%SiO₂ with meanδ¹⁸O = +6.0 ± 0.1. This¹⁸O enrichment can be explained in terms of differentiation of parental mafic magmas havingδ¹⁸O values between +5.7 to +6.2‰ through closed-system crystal fractionation because the lavas from all nine islands of the arc define a coherentδ¹⁸OSiO₂ trend. The S-isotope composition of oxidized magmas is not modified extensively through the degassing of SO₂; therefore, the meanδ³⁴S value of ca. +11‰ for the Mariana lavas is considered to be representative of their source region.The enrichment of¹⁸O and³⁴S in Mariana Arc parental magmas relative to ocean floor basalts withδ¹⁸O ca. + 5.7‰ andδ³⁴S = ca.0.3‰ is attributed to the recycling of¹⁸O- and³⁴S-rich crustal components (sediment withδ¹⁸O = ca. + 25‰ and seawater sulfate withδ³⁴S = ca. +20‰ into the upper mantle source region for these arc magmas. This interpretation is consistent with enrichments of radiogenic Sr and Pb in the same lavas relative to ocean-floor basalts erupted either side of the arc, which are presumed to share a common upper mantle source. This enrichment is considered to reflect the mixing of two components, one having a typical upper mantle composition and the other having a more radiogenic character similar to that of western Pacific pelagic sediments.     

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.     

Orographic controls on rain water isotope distribution in the Mount Lofty Ranges of South Australia

Hydrogen and oxygen isotopes of water are common environmental tracers used to investigate hydrological processes, such as evaporation, vegetation water use, surface water–groundwater interaction, and groundwater recharge. The water isotope signature in surface water and groundwater evolves from the initial rain signature. In mountain terrain, rain water stable isotope composition spatially varies due to complex orographic precipitation processes. Many studies have examined the isotope–elevation relationships, while few have quantitatively investigate the terrain aspect and slope effect on rain isotope distribution. In this paper, we examine the orographic effects more completely, including elevation, terrain slope and aspect, on stable isotope distribution in the Mount Lofty Ranges (MLR) of South Australia, using a multivariate regression model. The regression of precipitation isotope composition suggests that orographic effects are the dominant controls on isotope spatial variability. About 75% of spatial variability in δ¹⁸O and deuterium excess is represented by the regression using solely orography-related variables (elevation, terrain aspect and slope), with about 25% of δ¹⁸O spatial variability attributed to the terrain aspect and slope effect. The lapse rate is about −0.25‰ for every 100 m at both windward and leeward slopes. However, at the same elevation, δ¹⁸O at the leeward slope (eastern MLR) is 0.5‰ larger than that at the windward slope. The difference can be explained by different mechanisms – continuous rain-out processes on the windward side and sub-cloud evaporation on the leeward side. Both δ¹⁸O and deuterium excess maps (1 km resolution) are constructed based on the regression results for the MLR. Both maps are consistent with groundwater of local precipitation origin, and useful to examine groundwater recharge.     

Temperature dependence of the oxygen isotopic fractionation between diatom silica and water

We present a new paleotemperature scale, based on the oxygen isotopic ratio of the non-exchangeable fraction of the oxygen from diatom silica. The equation t = 17.2 − 2.4 (δ¹⁸O_silica − δ¹⁸O_water − 40) − 0.2 (δ¹⁸O_silica − δ¹⁸O_water − 40)² was derived using recent sediment samples from different oceanic areas, the temperature and isotopic composition of the local surface water. Comparison of our results with other relationships established for quartz-water or amorphous silica-water at higher temperature suggests no difference in isotopic fractionation between quartz-water and biogenic silica-water couples.     

Oxygen isotopic composition of alkaline anorogenic granites as a clue to their origin: the problem of crustal oxygen

The primary isotopic characteristics of alkaline granites are often obscured by secondary processes enhanced by their unusual chemical compositions. This is true for radiogenic as well as for stable isotopes. For example, the ⁸⁷Sr/⁸⁶Sr ratios can vary drastically in closed systems because of very high Rb/Sr ratios and can also be easily modified by direct or indirect interaction with continental crust because of low Sr concentrations. Moreover, the frequent occurrence of the granitic massifs as hypovolcanic complexes increases the probability of interaction with meteoric waters which is a common source of important isotopic variability.The investigation of oxygen isotope systematics in alkaline acidic rocks from various environments shows the¹⁸O content of their quartz to be highly invariable, and the δ¹⁸O values to be close to the mantle range of values. This is due to the resistance of quartz to isotopic exchange, which makes it a good tracer of primary isotopic composition. If we eliminate the quartz δ¹⁸O values for which interaction with meteoric water is well documented (five samples), the total range of variation (seventeen samples) is from 6.0 to 7.3‰ relative to SMOW. The values can easily be accounted for by, and correspond to, equilibrium with mantle-type material in a temperature range of 1200-800°C. If we consider possible effects of fractional crystallization, this temperature range can probably be reduced to its lower limit which is much more likely for rocks of acidic composition.The present oxygen isotope study strongly supports an origin for alkaline anorogenic granites from mantle-dominated sources.     

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.