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.     

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.     

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.     

Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

δ⁸⁷Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO₃-type groundwater prevails. δ⁸⁷Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ⁸⁷Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ⁸⁷Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ⁸⁷Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr²⁺. In contrast, more than 95% of Sr²⁺ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO₃-type groundwater. The surprisingly high content of carbonate-derived Sr²⁺ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.     

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.     

Hydrothermal silica chimney fields in the Galapagos Spreading Center at 86°W

Silica chimneys were discovered in 1985 at 86°W in the rift valley of the Galapagos Spreading Center at 2600 m depth (“Cauliflower Garden”). The inactive chimneys lack any sulfides and consist almost entirely of amorphous silica (up to 96 wt.% SiO₂, opal-A); Fe and Mn oxides are minor constituents. Oxygen isotope data show that formation of the silica chimneys took place at temperatures between 32°C (+29.9‰ δ¹⁸O) and 42°C (+27.8‰ δ¹⁸O).Th/Udating reveals a maximum age of 1440 ± 300y. Amorphous silica solubility relations indicate that the silica chimneys were formed by conductive cooling of pure hydrothermal fluids or by conductive cooling of a fluid/seawater mixture. Assuming equilibrium with quartz at 500 bars, initial fluid temperatures of more than 175°C (i.e., a concentration of > 182 ppm SiO₂) were required to achieve sufficient supersaturation for the deposition of amorphous silica at 40°C and 260 bars. If the silica chimneys originate from the same or a similar fluid as higher-temperature ( < 300°C) sulfide-silica precipitates found nearby (i.e., 2.5 km away), then subsurface deposition of sulfides may have occurred.     

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.     

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.     

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.).     

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.     

δCa evolution in a carbonate aquifer and its bearing on the equilibrium isotope fractionation factor for calcite

To improve understanding of Ca isotope transport during water-rock interaction on the continents, we measured dissolved δ⁴⁴Ca values along a 236 km flow path in the Madison aquifer, South Dakota, where fluids have chemically evolved according to dolomite and anhydrite dissolution, calcite precipitation, and Ca-for-Na ion-exchange over a timescale spanning ~ 15 kyr. We used a reactive transport model employing rate data constrained from major ion mass-balances to evaluate the extent to which calcite precipitation and ion-exchange fractionate Ca isotopes. Elevated δ⁴⁴Ca values during the initial and final stages of water transport possibly result from calcite precipitation under supersaturated conditions and Ca-for-Na ion-exchange, respectively. However, for the bulk of the flow path, δ⁴⁴Ca values evolve by mixing between anhydrite and dolomite dissolution, with no fractionation during calcite precipitation under saturated conditions. We attribute the absence of Ca isotope fractionation to the long timescale of water-rock interaction and slow rate of calcite precipitation, which have enabled fluids to chemically and isotopically equilibrate with calcite. We therefore conclude that the equilibrium Ca isotope fractionation factor between calcite and water (Δ_cal–w) is very close to zero. To the extent that the Madison aquifer typifies other groundwater systems where calcite slowly precipitates from solutions at or near chemical equilibrium, this study suggests that groundwater contributions to δ⁴⁴Ca variability on the continents can be modeled according to simple mixing theory without invoking isotope discrimination.     

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.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

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.     

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.     

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.     

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 aspects of iron oxide coagulation in water: Laboratory studies and implications for natural systems

Initial coagulation rates of colloidal hematite (-Fe₂O₃) particles (diameter less than 0.1 µm) were measured experimentally in well-defined laboratory systems at constant temperature. The relative stability ratio,W, was obtained at various ionic strengths in NaCl medium and at pH values in the range from 3 to 12. ExperimentalW values ranged from 1 to 10⁴ in various systems. The results delineate the roles ofspecific andgeneralized coagulation mechanisms for iron oxides. Among the specifically-interacting species (G _ads ⁰ >G _coul ⁰ ) studied were phosphate, monomeric organic acids of various structures, and polymeric organic acids. The critical coagulation-restabilization concentrations of specifically-interacting anions (from 10^–7 to 10^–4 molar) can be compared with the general effects of non-specific electrolyte coagulants (10^–3 to 10^–1 molar). The laboratory results are interpreted with the help of a Surface Complex Formation/Diffuse Layer Model (SCF/DLM) which describes variations of interfacial charge and potential resulting from variations of coagulating species in solution. Comparison of these laboratory experiments with observations on iron behavior in estuarine and lake waters aids in understanding iron removal mechanisms and coagulation time scales in natural systems.     

Roof-rock contamination of magma along the top of the reservoir for the Bishop Tuff

The Bishop Tuff, a well known Quaternary high-silica rhyolite in east-central California, is widely considered the type example of a vertically and monotonically zoned pyroclastic deposit that represents zoning in the source magma reservoir, inverted during the process of pyroclastic emplacement. However, the deposit of plinian pumice, which forms the base of the Bishop Tuff and represents the initial 10% or so of all magma erupted during the event that produced the Bishop Tuff, contains features at odds with monotonie zoning for the reservoir. Relative to overlying ignimbrite, the plinian deposit contains a reversal in trace-element zoning. Moreover, the ⁸⁷Sr/⁸⁶Sr is significantly higher than that in overlying ignimbrite (about 0.7084 vs 0.7064), and melt inclusions trapped in quartz phenocrysts exhibit notable variability of trace-element concentrations, even within a single host crystal (e.g., U: 10.77 to 8.91 ppm).These data have been previously interpreted as due to processes of chemical fractionation and evolution operating within a magma system closed to chemical interactions with its roof rocks. For example, the reversal in trace-element zoning has been explained by the first-erupted magma being erupted from somewhat below the top of a monotonically zoned reservoir. However, we submit that the reversed zoning and other above-noted features can be explained equally well as consequences of minor assimilation of roof rocks into a magma reservoir that was erupted from the top down.The basal part of the Bishop Tuff exhibits extreme concentrations and depletions of trace elements, relative to the average composition of crustal rocks. For example, the upward decrease of Sr in the Bishop magma reservoir (downward decrease in the ignimbrite) results in concentrations as low as 2–4 ppm. Because of the attendant ‘chemical leverage’, assimilation of < 1 wt.% of Sierra Nevada batholith rocks typical of the area could readily reverse an ‘uncontaminated’ Sr (and other trace elements) trend of zoning and could also substantially raise ⁸⁷Sr/⁸⁶Sr. Small-scale trace-element variability in the uppermost part of the Bishop magma reservoir, as recorded by the above-mentioned melt inclusions, may simply reflect melt heterogeneity produced by the process of assimilation.