Oxygen and carbon isotope evidence for seawater-hydrothermal alteration of the Macquarie Island ophiolite

Rocks of the Miocene Macquarie Island ophiolite, south of New Zealand, have oxygen and carbon isotopic compositions comparable to those of seafloor rocks. Basalt glass and weathered basalts have δ¹⁸O values at 5.8–6.0‰ and 7.9–9.5‰, respectively, similar to drilled seafloor rocks including samples from the Leg 29 DSDP holes near Macquarie Island. Compared to the basalt glass, the greenschist to amphibolite facies metaintrusives are depleted in¹⁸O (δ¹⁸O=3.2–5.9‰) similar to dredged seafloor samples, whereas the metabasalts are enriched (δ¹⁸O=7.1–9.7‰). Although the gabbros are only slightly altered in thin-section they have exchanged oxygen with a hydrothermal fluid to a depth of at least 4.5 km. There is an approximate balance between¹⁸O depletion and enrichment in the exposed ophiolite section. The carbon isotopic composition of calcite in the weathered basalts (δ¹³C=1.0–2.0‰) is similar to those of drilled basalts, but the metamorphosed rocks have low δ¹³C values (?14.6 to 0.9‰).These data are compatible with two seawater circulation regimes. In the upper regime, basalts were weathered by cold seawater in a circulation system with high water/rock ratios (?1.0). Based on calcite compositions weathering temperatures were less than 20°C and the carbon was derived from a predominantly inorganic marine source. As previously suggested for the Samail ophiolite, it is postulated that the lower hydrothermal regime consisted of two coupled parts. At the deeper levels, seawater circulating at low water/rock ratios (0.2–0.3) and high temperatures (300–600°C) gave rise to¹⁸O-depleted gabbro and sheeted dikes via open system exchange reactions. During reaction the seawater underwent a shift in oxygen isotopic composition (δ¹⁸O=1.0–5.0‰) and subsequently caused¹⁸O enrichment of the overlying metabasalts. In the shallower part of the hydrothermal regime the metabasalts were altered at relatively high water/rock ratios (1.0–10.0) and temperatures in the range 200–300°C. The relatively low water/rock ratios in the hydrothermal regime are supported by the low δ¹³C values of calcite, interpreted as evidence of juvenile carbon in contrast to the inorganic marine carbon found in the weathered basalts.     

Aragonite dissolution on the Bermuda pedestal: Its depth and geochemical significance

The depth distribution of pteropod and planktonic foram tests, and fine-grained (<62 μm) aragonite, high-Mg calcite (12 mode mol.% MgCO₃), and low-Mg calcite has been determined for surface sediments of an area of the eastern slope of the Bermuda pedestal. Over the range 1800–3000 m, fine-grained aragonite and fine-grained high-Mg calcite gradually disappear relative to fine-grained low-Mg calcite, and pteropods gradually disappear relative to planktonic forams. This is interpreted as preferential dissolution of aragonite (and high-Mg calcite) relative to low-Mg calcite over this depth range. Coarse aragonitic debris derived from shallow-water organisms living on the Bermuda platform does not show consistent disappearance over the same depth zone. Chemical analyses of bottom water samples taken at the same time as some of the sediment samples indicate that the degree of saturation with respect to aragonite Ω_A over the zone of aragonite disappearance ranges from 0.55 to 0.85; i.e. major dissolution occurs only at Ω_A values distinctly less than one. These results lend credence to the hypothesis that CaCO₃ dissolution in the oceans, both as aragonite and as calcite, takes place mainly as a response to complex chemical kinetic phenomena and not as a result of the simple attainment of undersaturation (thermodynamic hypothesis) or the resuspension of bottom sediment (hydrodynamic hypothesis).     

Uranium loss and aragonite–calcite age discordance in a calcitized aragonite stalagmite

We analyzed uranium-series concentrations and isotopic ratios in a mixed aragonite and calcite stalagmite from Juxtlahuaca Cave, from the Sierra Madre del Sur of Mexico. The U-series data for the aragonite layers return highly precise and stratigraphically correct ages over the past ca. 4300 years. In contrast, age determinations from calcite layers are too old by several hundred years relative to the precise aragonite ages, have analytical uncertainties an order of magnitude larger than aragonite ages, and yield ages that do not overlap the aragonite ages within analytical uncertainties. Based on geochemical and petrographic observations, we interpret the calcite layers to have formed from recrystallization of aragonite soon after primary aragonite deposition. Calcite occurs as discontinuous lenses on and off the growth axis, and laminae can be traced between aragonite and calcite layers, demonstrating that visible growth banding is not effaced in the recrystallization process. Paired aragonite-calcite U-series data from coeval stratigraphic layers demonstrate that uranium concentrations decrease by two orders of magnitude during calcitization, and result in decreased (²³⁴U/²³⁸U). Uranium loss during diagenesis mimics a need for an age correction using an initial ²³⁰Th/²³²Th ratio one to two orders of magnitude larger than the bulk Earth ratio of 4.4 ± 2.2 × 10⁻⁶. A need for apparent high initial ²³⁰Th/²³²Th ratios results from ingrowth of ²³⁰Th during ²³⁴U decay.     

Ages and composition of gas trapped in Allan Hills and Byrd core ice

Gas is extracted from large (6–31 kg) Antarctic ice samples to obtain sufficient CO₂ for¹⁴C measurements with small low-level proportional counters. The¹⁴C ages of Byrd core ice are in accord with glaciological estimates ranging from (2.2_−1.1^+1.4)×10³ yr at 271 m depth to more than 8 × 10³ yr at 1071 m depth. The CO₂ abundances in gas extracted from Byrd core ice range from 0.0216 to 0.051%, with below present-day atmosphere CO₂ abundances for ice from 1068 and 1469 m depths. The CO₂ abundance in gas from Allan Hills surface ice samples ranges between four and six times the atmospheric value and the CO₂ had a specific activity three times that of contemporary carbon. A possible explanation for the anomalously high specific activity is surface melting with the incorporation into CO₂ of¹⁴C produced by cosmic ray spallation of oxygen in ice. The CO₂ abundance in gas extracted from subsurface Allan Hills ice ranged from 0.030 to 0.065%, and the specific activities are below contemporary carbon, indicating ages greater than 5×10³ yr. The¹⁸O/¹⁶O ratio of oxygen in the trapped gas is the same as that of atmospheric oxygen and differs markedly from the¹⁸O/¹⁶O ratio in the ice. The O₂, N₂, and Ar abundances and isotopic compositions are similar to those in contemporary air, except for positive¹⁵N/¹⁴N ratios in a few samples.     

Weathering,Sr fluxes,and controls on water chemistry in the Lake Qinghai catchment,NE Tibetan Plateau

Strontium (Sr) concentrations and isotopic ratios have been measured in a series of water and rock samples from most of the major tributaries of the Lake Qinghai basin on the north‐eastern Tibetan Plateau. Dissolved Sr and ⁸⁷Sr/⁸⁶Sr show ranges of 488–12 240 nmol/l and 0·710497–0·716977, respectively. These data, together with measurements of major cations and anions in rivers and their tributaries and various lithologies of the catchment, were used to determine the contributions of Sr and its isotopic expense to rivers and lakes. Our results demonstrate that the chemical components and ⁸⁷Sr/⁸⁶Sr ratios of the alkaline waters are derived from mixing of carbonate and silicate sources, with the former contributing 72 ± 18% dissolved Sr to rivers. The difference in tributary compositions stems from the lithology of different river systems and low weathering intensity under a semi‐arid condition. Variation in ⁸⁷Sr/⁸⁶Sr ratios places constraint on the Sr‐isotopic compositions of the main tributaries surrounding Lake Qinghai. The water chemistry of the Buha River, the largest river within the catchment underlain by the late Paleozoic marine limestone and sandstones, dominates Sr isotopic composition of the lake water, being buffered by the waters from the other rivers and probably by groundwater. However, the characteristic chemical composition of the lake itself differs remarkably from the rivers, which can be attributed to precipitation of authigenic carbonates (low‐magnesium calcite, aragonite, and dolomite), though this does not impact the Sr isotope signature, which may remain a faithful indicator in paleo‐records. Regarding the potential role of groundwater input within the Lake Qinghai systems in the water budget and water chemistry, we have also determined the Sr concentration and ⁸⁷Sr/^S6Sr ratio of groundwater from diverse environments. This has allowed us to further constrain the Sr isotope systematic of this source. A steady‐state calculation gives an estimate for the groundwater flux of 0·19 ± 0·03 × 10⁸ m³/yr, accounting for about 8% of contemporary lake Sr budget. Copyright © 2010 John Wiley & Sons, Ltd.     

SOIL FINGERPRINTING IN THE PALOUSE BASIN, USA USING STABLE CARBON AND NITROGEN ISOTOPES

1 INTRODUCTION Watershed restoration efforts have been accelerated in recent years by mandates in the Clean Water Act, the Endangered Species Act, and increasing pressure from environmental groups (Wagner and Roberts, 1998). To address these mandates, water-quality management plans and Total Maximum Daily Loads (TMDLs) have been developed for surface waters, such as streams placed on the 303(d) list because of beneficial use impairment. Commonly, much of the degradation of surface…     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

The hydrothermal system of Nevado del Ruiz volcano,Colombia

Hot springs and steam vents on the slopes of Nevado del Ruiz volcano provide evidence regarding the nature of hydrothermal activity within the summit and flanks of the volcano. At elevations below 3000 m, alkali-chloride water is discharged from two groups of boiling springs and several isolated warm springs on the western slope of Nevado del Ruiz. Chemical and isotopic geothermometers suggest that the boiling springs are fed by an aquifer having a subsurface equilibration temperature of at least 175°C, and the sampled warm spring is fed by an aquifer having a subsurface equilibration temperature near 150°C. Similarities in conservative solute ratios (e.g., B/Cl) indicate that the alkali-chloride waters may be related to a single reservoir at depth. Isotopic ratios of hydrogen and oxygen indicate that recharge for the alkali-chloride aquifers comes mostly from higher elevations on the volcano. Steam vents and steam-heated bicarbonate-sulfate springs at higher elevations, along a linear structural trend with the alkali-chloride springs, may be derived partly from the alkali-chloride water at depth by boiling. Steam from the vents (84°C) yields a gas geothermometer temperature of 209°C. Acid-sulfate-chloride and acid-sulfate waters are discharged widely from warm springs above 3000 m on the northern and eastern slopes of Nevado del Ruiz. Similarities in B/Cl and SO₄/Cl ratios suggest that the acid waters are mixtures of water from an acid-sulfate-chloride reservoir with various proportions of shallow, dilute groundwater. The major source of sulfate, halogens, and acidity for the acid waters may be high-temperature magmatic gases. Available data on hot spring temperatures and compositions indicate that they have remained fairly stable since 1968. However, the eruption of November 13, 1985 apparently caused an increase in sulfate concentration in some of the acid springs that peaked about a year after the eruption. Long-term monitoring of hot spring compositions over many years will be required to better define the effects of volcanic activity on the Nevado del Ruiz hydrothermal system.     

The isotopic composition of oxygen and carbon in the hyaloclastites from the Mt. Iblei volcanic area,Eastern Sicily: A preliminary study

Oxygen and carbon isotopic analyses were carried out for some typical submarine volcanic products (a lava flow, a pillow fragment and four hyaloclastite breccias) from the northwestern zone of the Mt. Iblei volcanic complex, eastern Sicily. The δ¹⁸O value of the perental basaltic magma (6.0 ± 0.2‰), estimated from the analyses of some fresh unaltered glassy samples of various type, lies in the values range of primary basalts. Appreciably higher δ¹⁸O values, probably due to low-temperature exchanges with sea water, have been found for lava samples and the interior of the pillow fragment. The δ¹⁸O and δ¹³C of the calcites of the groundmass of the hyaloclastite samples, ranging from 30.59 to 33.65 and from ?2.99 to 0.46‰ respectively, are typical of low-temperature marine carbonates. Because calcite is one of the last minerals to form. these results suggest that the hyaloclastites studied formed entirely in a submarine environment. The¹⁸O/¹⁶O ratios recorded in the silicate portions of the matrices of the hyaloclasites (δ¹⁸O=13.99 to 16.61) are interpreted as the result of halmyrolytic processes occurring at temperatures somewhat higher than that of the sea floor.     

230Th/234U and 14C dating of a lowstand coral reef beneath the insular shelf off Irabu Island, Ryukyus, southwestern Japan

Abstract   High-resolution seismic reflection profiles delineated the distribution of mound-shaped reflections, which were interpreted as reefs, beneath the insular shelf western off Irabu Island, Ryukyus, southwestern Japan. A sediment core through one of the mounded structures was recovered from the sea floor at a depth of −118.2 m by offshore drilling and was dated by radiometric methods. The lithology and coral fauna of the core indicate that the mounded structure was composed of coral–algal boundstone suggesting a small-scaled coral reef. High-precision α-spectrometric ²³⁰Th/²³⁴U dating coupled with calibrated accelerator mass spectrometric ¹⁴C ages of corals obtained reliable ages of this reef ranging from 22.18 ± 0.63 to 30.47 ± 0.98 ka. This proves that such a submerged reef was formed during the lowstand stage of marine oxygen isotope stages 3–2. The existence of low-Mg calcite in the aragonitic coral skeleton of 22.18 ± 0.63 ka provides evidence that the reef had once been exposed by lowering of the relative sealevel to at least −126 m during the last glacial maximum in the study area. There is no room for doubt that a coral reef grew during the last glacial period on the shelf off Irabu Island of Ryukyus in the subtropical region of western Pacific.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Depositional history of Luna 24 drill core soil samples

Six soil samples from various depths of the Luna 24 drill core column have been analysed for their particle track records and light noble gas compositions. The observed particle track records indicate higher degree of maturity for the upper zone (～1 m) of this regolith column as compared to the soils in the lower zone (～0.4 m). The cosmogenic²¹Ne concentrations decrease rapidly with depth to 1 m, after which the concentrations level off or increase slightly. These data suggest a multi-stage depositional history for this drill core soil column consisting of: (1) rapid deposition of regolith material, (2) a cratering event about 400 m.y. B.P., leading to excavation to a depth of ～1 m from the present regolith surface, (3) a relatively rapid fill up of the crater with near-surface irradiated material, and (4) in-situ irradiation during the last about 250–300 m.y. Such a depositional sequence can also explain the observed lack of correlation between different surface exposure-correlated maturity indices in these drill core soil samples.     

Strontium and oxygen isotopic composition of some basalts from Hole 504B,Costa Rica Rift,DSDP Legs 69 and 70

Seventeen whole-rock samples, generally taken at 25–50 m intervals from 5 to 560 m sub-basement in Hole 504B, drilled in 6.2 m.y. old crust, were analysed for⁸⁷Sr/⁸⁶Sr ratios, Sr and Rb concentrations, and¹⁸O/¹⁶O ratios. Sr isotope ratios for 8 samples from the upper 260 m of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the 330–560 m interval, 5 samples have a restricted range of 0.70255–0.70279, with a mean of 0.70266, the average value for fresh mid-ocean ridge basalts (MORB). In the 260–330 m interval, approximately intermediate Sr isotopic ratios are found.δ¹⁸O values (‰) range from 6.4 to 7.8 in the upper 260 m, 6.2–6.4 in the 270–320 m interval, and 5.8–6.2 in the 320–560 m interval. The values in the upper 260 m are typical for basalts which have undergone low-temperature seawater alteration, whereas the values for the 320–560 m interval correspond to MORB which have experienced essentially no oxygen isotopic alteration.The higher⁸⁷Sr/⁸⁶Sr and¹⁸O/¹⁶O ratios in the upper part of the hole can be interpreted as the result of a greater overall water/rock ratio in the upper part of the Hole 504B crust than in the lower part. Interaction of basalt with seawater(⁸⁷Sr/⁸⁶Sr=0.7091) increased basalt⁸⁷Sr/⁸⁶Sr ratios and produced smectitic alteration products which raised whole-rock δ¹⁸O values. Seawater circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below about 230 m sub-basement. These flows may have helped to seal off lower basalts from through-flowing seawater.     

Noble gas systematics of deep rift zone glasses from Loihi Seamount, Hawaii

We report new noble gas fusion and crushing data for six pillow rim glasses, recovered between 3 and 5 km water depth on the south rift zone of Loihi Seamount, Hawaii. Helium abundances of the glasses vary from 0.3 to 2.3 μcc/g, with ⁴He/³He ratios between 30000 and 27000 (24–27 R_A), similar to previously reported values. The neon data form a correlation line which is similar to the Loihi-Kilauea line reported by Honda et al. [1], but extends to much higher ratios, up to 12.9 and 0.0382 for the ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios, respectively. This provides conclusive evidence for the suggestion that the Hawaiian plume, thought to originate in the lower mantle, has a solar-like ²⁰Ne/²²Ne composition [1], but a slightly higher ²¹Ne/²²Ne ratio. ⁴⁰Ar/³⁶Ar ratios of the deep rift-zone glasses are as high as 2600, and show a positive correlation with neon isotopic ratios. In contrast to neon and argon, all xenon isotopic compositions are isotopically indistinguishable from air, which either suggests preferential atmospheric contamination of xenon, or could indicate an atmospheric xenon isotopic composition for the lower mantle.     

High-resolution terrestrial carbon isotope and planktic foraminiferal records of the Upper Cenomanian to the Lower Campanian in the Northwest Pacific

Making Upper Cretaceous biostratigraphic correlations between the Northwest Pacific and Tethyan–Atlantic sections have been difficult because of rare frequencies of age-diagnostic macro- and microfossils in the sequences in the Northwest Pacific region. In order to correlate these sections precisely, an integrated planktic foraminiferal and bulk wood carbon-isotope stratigraphy from the upper Cenomanian to the lower Campanian succession (the middle–upper part of the Yezo Group) of Hokkaido, northern Japan is established with an average resolution of 50 k.y. The δ¹³C curves from bulk wood of the Yezo Group and from bulk carbonate of English Chalk show remarkably similar patterns of isotopic fluctuation, allowing the correlation of 22 carbon isotopic events between these sections. This high-resolution correlation greatly improves the previous micro- and macrofossil biostratigraphic schemes in the Northwest Pacific region, and reveals that global events, such as the oxygen depletion at the OAE 2 horizon, the constant decrease in pCO₂ during the Late Cretaceous, and the eustatic sea-level falls in the late middle Turonian, Santonian/Campanian Boundary and early Campanian, are recorded in the Upper Cretaceous sequence of the Northwest Pacific.     

He and Ne isotopes in oceanic crust: implications for noble gas recycling in the mantle

In an attempt to determine the helium and neon isotopic composition of the lower oceanic crust, we report new noble gas measurements on 11 million year old gabbros from Ocean Drilling Program site 735B in the Indian Ocean. The nine whole rock samples analyzed came from 20 to 500 m depth below the seafloor. Helium contents vary from 3.3×10⁻¹⁰ to 2.5×10⁻⁷ ccSTP/g by crushing and from 5.4×10⁻⁸ to 2.4×10⁻⁷ ccSTP/g by melting. ³He/⁴He ratios vary between 2.2 and 8.6 Ra by crushing and between 2.9 and 8.2 by melting. The highest R/Ra ratios are similar to the mean mid-ocean ridge basalt (MORB) ratio of 8±1. The lower values are attributed to radiogenic helium from in situ α-particle production during uranium and thorium decay. Neon isotopic ratios are similar to atmospheric ratios, reflecting a significant seawater circulation in the upper 500 m of exposed crust at this site. MORB-like neon, with elevated ²⁰Ne/²²Ne and ²¹Ne/²²Ne ratios, was found in some high temperature steps of heating experiments, but with very small anomalies compared to air. These first results from the lower oceanic crust indicate that subducted lower oceanic crust has an atmospheric ²⁰Ne/²²Ne ratio. Most of this neon must be removed during the subduction process, if the ocean crust is to be recirculated in the upper mantle, otherwise this atmospheric neon will overwhelm the upper mantle neon budget. Similarly, the high (U+Th)/³He ratio of these crustal gabbros will generate very radiogenic ⁴He/³He ratios on a 100 Ma time scale, so lower oceanic crust cannot be recycled into either MORB or oceanic island basalt without some form of processing.     

Nickel isotopic studies in meteorites

We have analyzed the nickel isotopic composition of meteoritic materials by high-precision mass spectrometry. The samples analyzed include almost all meteorite types for which large isotopic anomalies have been reported for oxygen, silver, magnesium and titanium. These samples are C₁, C₃, L, LL, H and E chondrites, IVB irons, Eagle Station pallasite and inclusion, matrix and “whole rock” samples of the Allende meteorite. The result is that we have not found any anomaly for nickel isotopic compositions within our accuracy of 0.7‰ for⁶¹Ni/⁶⁰Ni, 0.4-0.08‰ for⁶²Ni/⁶⁰Ni and 1–1.5‰ for⁶⁴Ni/⁶⁰Ni.     

Oxygen isotopic composition of low-temperature authigenic clinoptilolite

Oxygen isotope ratios were obtained from authigenic clinoptilolites from Barbados Accretionary Complex, Yamato Basin, and Exmouth Plateau sediments (ODP Sites 672, 797, and 762) in order to investigate the isotopic fractionation between clinoptilolite and pore water at early diagenetic stages and low temperatures. Dehydrated clinoptilolites display isotopic ratios for the zeolite framework (δ¹⁸O_f) that extend from +18.7‰ to +32.8‰ (vs. SMOW). In combination with associated pore water isotope data, the oxygen isotopic fractionation between clinoptilolite and pore fluids could be assessed in the temperature range from 25°C to 40°C. The resulting fractionation factors of 1.032 at 25°C and 1.027 at 40°C are in good agreement with the theoretically determined oxygen isotope fractionation between clinoptilolite and water. Calculations of isotopic temperatures illustrate that clinoptilolite formation occurred at relatively low temperatures of 17°C to 29°C in Barbados Ridge sediments and at 33°C to 62°C in the Yamato Basin. These data support a low-temperature origin of clinoptilolite and contradict the assumption that elevated temperatures are the main controlling factor for authigenic clinoptilolite formation. Increasing clinoptilolite δ¹⁸O_f values with depth indicate that clinoptilolites which are now in the deeper parts of the zeolite-bearing intervals had either formed at lower temperatures (17–20°C) or under closed system conditions.     

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.