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.     

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.     

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.     

Trapped solar and cosmogenic noble gas abundances in Apollo 15 and 16 deep drill samples

Abundances and isotopic compositions of all the stable noble gases have been measured in 19 different depths of the Apollo 15 deep drill core, 7 different depths of the Apollo 16 deep drill core, and in several surface fines and breccias. All samples analyzed from both drill cores contain large concentrations of solar wind implanted gases, which demonstrates that even the deepest layers of both cores have experienced a lunar surface history. For the Apollo 15 core samples, trapped⁴He concentrations are constant to within a factor of two; elemental ratios show even greater similarities with mean values of⁴He/²²Ne= 683±44,²²Ne/³⁶Ar= 0.439±0.057,³⁶Ar/⁸⁴Kr= 1.60±0.11·10³, and⁸⁴Kr/¹³²Xe= 5.92±0.74. Apollo 16 core samples show distinctly lower⁴He contents,⁴He/²²Ne(567±74), and²²Ne/³⁶Ar(0.229±0.024), but their heavy-element ratios are essentially identical to Apollo 15 core samples. Apollo 16 surface fines also show lower values of⁴He/²²Ne and²²Ne/³⁶Ar. This phenomenon is attributed to greater fractionation during gas loss because of the higher plagioclase contents of Apollo 16 fines. Of these four elemental ratios as measured in both cores, only the²²Ne/³⁶Ar for the Apollo 15 core shows an apparent depth dependance. No unambiguous evidence was seen in these core materials of appreciable variations in the composition of the solar wind. Calculated concentrations of cosmic ray-produced²¹Ne,⁸⁰Kr, and¹²⁶Xe for the Apollo 15 core showed nearly flat (within a factor of two) depth profiles, but with smaller random concentration variations over depths of a few cm. These data are not consistent with a short-term core accretion model from non-irradiated regolith. The Apollo 15 core data are consistent with a combined accretion plus static time of a few hundred million years, and also indicate variable pre-accretion irradiation of core material. The lack of large variations in solar wind gas contents across core layers is also consistent with appreciable pre-accretion irradiation. Depth profiles of cosmogenic gases in the Apollo 16 core show considerably larger concentrations of cosmogenic gases below ～65 cm depth than above. This pattern may be interpreted either as an accretionary process, or by a more recent deposition of regolith to the upper ～70 cm of the core. Cosmogenic gas concentrations of several Apollo 16 fines and breccias are consistent with ages of North Ray Crater and South Ray Crater of ～50·10⁶ and ～2·10⁶ yr, respectively.     

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.     

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…     

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 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.     

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.     

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.     

Carbon isotope composition and comparison of Lower Triassic marine carbonate rocks from Southern Longmenxia section in Guang’an,Sichuan Basin

The Early Triassic was a period of ecological restoration for the earth's system after the end-Permian mass extinction.Geochemical records linked to the variations in marine ecosystems during this period have attracted the interest of geologists for many years.Based on petrographic analysis of samples and evaluations of their reliability as proxies for original seawater,this study investigated the carbon and oxygen isotopic compositions of 350 carbonate rock samples from the Lower Triassic(and adjacent strata)in the southern Longmenxia section of Guang'an,eastern Sichuan Basin.The results indicate that the Triassic carbonate rocks from the southern Longmenxia section favorably preserved the original seawater'sδ~(13)C signal.Furthermore,carbon and oxygen isotopic compositions are found to be poorly correlated,with a determination coefficient as low as 0.0205 and only 44 rock samples show results of Mn/Sr2 and/orδ~(18)0-6.5‰.The complete carbon isotopic curve for the Lower Triassic is established using the data from the remaining 306 samples with Mn/Sr2 and/orδ~(18)O-6.5‰.This curve presents favorable comparability on a global scale,specifically in theδ~(13)C minima near the Permian-Triassic boundary,at the top of the Jia1 and within the the Jia3,as well as in theδ~(13)C maxima at the tops of the Ye1 and Ye4,at the base of the Jia2 and at the top of the Ye3.The peaks and troughs corresponding to these maxima and minima all reflect global signals.By comparing these results to previous research on coeval carbon isotopic curves established within the chronostratigraphic framework,the ages of these critical evolution points are determined.The results show that the Ye1 roughly corresponds to the Griesbachian substage;the Ye2 through Ye4 correspond to the Dienerian substage;Jial corresponds to the Smithian substage;from the Jia2 to the lower part of the Jia4 correspond to the Spathian substage;and the middle and upper parts of the Jia4 belongs to the Aegean Substage of the Middle Triassic.Around the boundary between the Jial and Jia2(which represents the Smithian-Spathian boundary(SSB)),the value ofδ~(13)C increases rapidly from-0.911‰to 3.679‰.The span during which the seawater's carbon isotope experiences this drastic change may be less than36 kyr.The oxygen isotope,which is more sensitive to sedimentary environmental changes,exhibits changes prior to the carbon isotope near the SSB,indicating a significant increase in the salinity of the seawater before a sharp rise in the carbon isotope;this event leads to the formation of evaporites and dolomites.     

The ReOs systematics of the Ronda Ultramafic Complex of southern Spain

The Os isotopic compositions of twelve ultramafic and six mafic layer samples from the Ronda Ultramafic Complex of southern Spain have been determined. Among the ultramafic rocks, ¹⁸⁷Os/¹⁸⁶Os varies from 0.98 to 1.12. A weak correlation is observed between ¹⁸⁷Os/¹⁸⁶Os and Re/Os. A much stronger correlation exists between Os isotopic ratio and Mg#, suggesting that the Re/Os ratios have been perturbed to some extent. Two alternatives are proposed to explain the relationship between Os composition and Mg#: (1) Continuous processes in the convecting mantle; (2) Radiogenic ingrowth since an ancient melt depletion event. No relationship is observed between ¹⁸⁷Os/¹⁸⁶Os and ¹⁴³Nd/¹⁴⁴Nd. This is probably because the Nd systematics were strongly affected by a recent metasomatic event, which apparently had little effect on the Os isotopic compositions.The Os isotopic ratios of the mafic layers range from 1.7 to 47.9. Within a single thick layer, the ratios vary from 16.5 to 47.9. These high ratios demonstrate that the layers are ancient features. Among the mafic samples, Os isotopic ratio is found to decrease strongly with increasing Os concentration, which ranges from 0.009 ppb to 1.16 ppb. One layer, which had a SmNd model age of less than 200 Ma, yielded a ReOs model age of about 2 Ga. This implies that neither system can be trusted to give accurate information about the time of mafic layer formation.     

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.     

Source of lead in Central American and Caribbean mineralization,II. Lead isotope provinces

In an earlier study of Mesozoic and Cenozoic mineralization in Central America and the Caribbean region, we found that lead isotopic compositions of deposits in northern Central America, which is underlain by a pre-Mesozoic craton, ranged to higher²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb compositions than did deposits from elsewhere in the region, where the basement is Mesozoic oceanic material. Using 16 analyses for 12 new deposits, as well as new analyses for 11 of the samples studied previously, we have found that lead isotopic compositions correlate closely with crustal type but show little or no correlation with depth to the M-discontinuity. The deposits are divisible into three main groups including (in order of increasing²⁰⁷Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb ratio): (1) deposits in southern Central America and all deposits in the Greater Antilles except Cuba; (2) all deposits in northern Central America; and (3) the Cuban deposits. Southern Central American and Caribbean lead is higher in²⁰⁷Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb than most mid-ocean ridge basalts but could have been derived directly or indirectly from undepleted mantle. Northern Central America can be divided into the Maya block, which belongs to the Americas plate, and the Chortis block, which belongs to the Caribbean plate. Maya block deposits fall along a linear array whereas those of the Chortis block (except the Monte Cristo deposit) form a cluster. These results suggest that the Maya block is underlain by crust or mantle with a large range of U/Pb and Th/U ratios, whereas the Chortis block basement is more homogeneous. Two-stage model calculations indicate an age of about 2280±310 m.y. for the Maya block basement, although no such rocks are known in the region. Comparison of the Chortis block data to our recently published lead isotopic analyses of Mexican deposits shows considerable similarities suggesting that the Chortis block could have been derived from Mexico.     

Noble gas isotopic abundances and noble metal concentrations in sediments from the Cretaceous-Tertiary boundary

Noble gases in four sediment samples from the Cretaceous-Tertiary boundary collected near Stevns in Denmark were investigated to test the possibility of the presence of noble gases indicative for meteorites. All samples were also analyzed for the noble metals Os and Ir and twelve other elements. The observed enrichments of³He,⁴He and of Ar, Kr, and Xe relative to atmospheric abundances can be explained without invoking the addition of extraterrestrial material. The ²⁰Ne/²²Ne ratio and the Kr and Xe isotopic compositions are identical with the isotopic ratios in the terrestrial atmosphere. In contrast, the high noble metal concentrations indicate the presence of material with elemental abundances similar to chondritic matter. Compared to noble metals the noble gases are less sensitive tracers of an admixture of extraterrestrial matter in sediments.