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1.
Diamonds from high- and low-MgO groups of eclogite xenoliths from the Jericho kimberlite, Slave Craton, Canada were analyzed for carbon isotope compositions and nitrogen contents. Diamonds extracted from the two groups show remarkably different nitrogen abundances and δ13C values. While diamonds from high-MgO eclogites have low nitrogen contents (5-82 ppm) and extremely low δ13C values clustering at ∼−40‰, diamonds from the low-MgO eclogites have high nitrogen contents (>1200 ppm) and δ13C values from −3.5‰ to −5.3‰.Coupled cathodoluminescence (CL) imaging and SIMS analysis of the Jericho diamonds provides insight into diamond growth processes. Diamonds from the high-MgO eclogites display little CL structure and generally have constant δ13C values and nitrogen contents. Some of these diamonds have secondary rims with increasing δ13C values from −40‰ to ∼−34‰, which suggests secondary diamond growth occurred from an oxidized growth medium. The extreme negative δ13C values of the high-MgO eclogite diamonds cannot be produced by Rayleigh isotopic fractionation of average mantle-derived carbon (−5‰) or carbon derived from typical organic matter (∼−25‰). However, excursions in δ13C values to −60‰ are known in the organic sedimentary record at ca. 2.7 and 2.0 Ga, such that diamonds from the high-MgO eclogites could have formed from similar organic matter brought into the Slave lithospheric mantle by subduction.SIMS analyses of a diamond from a low-MgO eclogite show an outer core with systematic rimwards increases in δ13C values coupled with decreases in nitrogen contents, and a rim with pronounced alternating growth zones. The coupled δ13C-nitrogen data suggest that the diamond precipitated during fractional crystallization from an oxidized fluid/melt from which nitrogen was progressively depleted during growth. Model calculations of the co-variation of δ13C-N yielded a partition coefficient (KN) value of 5, indicating that nitrogen is strongly compatible in diamond relative to the growth medium. δ13C values of diamond cores (−4‰) dictate the growth medium had higher δ13C values than primary mantle-derived carbon. Therefore, possible carbon sources for the low-MgO eclogite diamonds include oxidized mantle-derived (e.g. protokimberlite or carbonatite) fluids/melts that underwent some fractionation during migration or, devolatilized subducted carbonates.  相似文献   

2.
In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (3He/4He = 4-6 Ra, 40Ar/36Ar = 20,000-30,000, δ13C = −4.5‰ to −6.9‰ and δ15N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high 36Ar content of the diamonds (>1 × 10−9 cm3/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the 36Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10−12 cm3/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.  相似文献   

3.
Isotopic and geochemical evidence of paleoclimates, especially for the last glaciation, has been obtained from deep confined groundwaters of southern India. The δ13C, δ18O, chloride, and deuterium analyses of groundwaters show distinct excursions inferred to be related to climatic variations. The arid climatic episode associated with the last glaciation (18,000 ± 2000 yr B.P.) is conspicuously identified by signatures of relatively enriched δ13C (−10 to −12‰ PDB) and δ18O (−5.3 to −4.8‰ SMOW) values, and high chloride concentration (80 to 160 mg/l). The transition from an arid to humid period ca. 12,000–8000 yr B.P. is shown by a decreasing trend in the δ13C (−9.5 to −17‰) and δ18O (−4.5 to −6.3‰) contents of groundwaters. The late Holocene (since 4000 yr B.P.), marked by a more humid but unstable climate, is identified by further depletion of δ13C (−13 to −20‰) and δ18O (−5.2 to −6.3‰). Similar variation between δ18O and chloride values in confined groundwaters further demonstrates two distinct climatic excursions (arid and humid) governed by the “amount effect.” This is the first time that isotopic and geochemical signatures related to changing paleoclimates have been identified in the confined groundwaters of the southern Indian landmass.  相似文献   

4.
13C/12C and 18O/16O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ18O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ13C values ranged from −13.2‰ to 0.0‰. δ18O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ18O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ18O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ13C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ13C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C3, C4) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.  相似文献   

5.
Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ18O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ18O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ18O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ18O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ13C value of the Fe(CO3)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO2 derived primarily from oxidation of relict Eocene wood with δ13C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of 13C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ18O record of the latest Miocene/Pliocene Arctic climate.  相似文献   

6.
We present whole rock Li and Mg isotope analyses of 33 ultramafic xenoliths from the terrestrial mantle, which we compare with analyses of 30 (mostly chondritic) meteorites. The accuracy of our new Mg isotope ratio measurement protocol is substantiated by a combination of standard addition experiments, the absence of mass independent effects in terrestrial samples and our obtaining identical values for rock standards using two different separation chemistries and three different mass-spectrometric introduction systems. Carbonaceous, ordinary and enstatite chondrites have irresolvable mean stable Mg isotopic compositions (δ25Mg = −0.14 ± 0.06; δ26Mg = −0.27 ± 0.12‰, 2SD), but our enstatite chondrite samples have lighter δ7Li (by up to ∼3‰) than our mean carbonaceous and ordinary chondrites (3.0 ± 1.5‰, 2SD), possibly as a result of spallation in the early solar system. Measurements of equilibrated, fertile peridotites give mean values of δ7Li = 3.5 ± 0.5‰, δ25Mg = −0.10 ± 0.03‰ and δ26Mg = −0.21 ± 0.07‰. We believe these values provide a useful estimate of the primitive mantle and they are within error of our average of bulk carbonaceous and ordinary chondrites. A fuller range of fresh, terrestrial, ultramafic samples, covering a variety of geological histories, show a broad positive correlation between bulk δ7Li and δ26Mg, which vary from −3.7‰ to +14.5‰, and −0.36‰ to + 0.06‰, respectively. Values of δ7Li and δ26Mg lower than our estimate of primitive mantle are strongly linked to kinetic isotope fractionation, occurring during transport of the mantle xenoliths. We suggest Mg and Li diffusion into the xenoliths is coupled to H loss from nominally anhydrous minerals following degassing. Diffusion models suggest that the co-variation of Mg and Li isotopes requires comparable diffusivities of Li and Mg in olivine. The isotopically lightest samples require ∼5-10 years of diffusive ingress, which we interpret as a time since volatile loss in the host magma. Xenoliths erupted in pyroclastic flows appear to have retained their mantle isotope ratios, likely as a result of little prior degassing in these explosive events. High δ7Li, coupled with high [Li], in rapidly cooled arc peridotites may indicate that these samples represent fragments of mantle wedge that has been metasomatised by heavy, slab-derived fluids. If such material is typically stirred back into the convecting mantle, it may account for the heavy δ7Li seen in some oceanic basalts.  相似文献   

7.
In the Czech-German border region of the Vogtland and NW Bohemia (western Eger rift, Central Europe), chemical and isotopic compositions (C, N, He, Ar) of free gas from a thermal water escape (fluorite mine, Schönbrunn), two mineral springs (“Eisenquelle,” Bad Brambach; “Sprudel III,” Bad Elster) and a mofette (Bublak) located along an ∼40-km long traverse are reported. The gases of Bublak and Bad Brambach are CO2-rich (>99 vol.%) and have δ13C values of −1.95 and −4.29‰, respectively. With distance from the center of CO2 degassing (Bublak) the δ13C values decrease, most likely due to physico-chemical fractionation of CO2 between gaseous and aqueous phases rather than to admixture of organic/biogenic CO2. The δ15N values range between −3.2 and −0.6‰, compared to an upper mantle value of −4.0 ± 1.0‰. The four locations are characterized by 3He/4He ratios decreasing from 5.9 Ra in the center (Bublak) to 0.8 Ra in the periphery (Schönbrunn) and give evidence for mixing of He from a deep-seated magmatic source with a crustal source. The location with the highest 3He/4He ratio (5.9 Ra) is accompanied by the highest 40Ar/36Ar (550). We argue that the nitrogen of the Bublak mofette gas is a mixture of predominantly atmospheric and mantle-derived components, whereas at the other three locations crustal nitrogen may also be present. The Bublak δ15N value of ≈−4.5 ± 1.0‰ represents the first free gas δ15N reference from the European subcontinental mantle (ESCM) and indicates that, in contrast to the 3He/4He ratios, the δ15N values are equal for ESCM and MORB, respectively.  相似文献   

8.
At Lucky Strike near the Azores Triple Junction, the seafloor setting of the hydrothermal field in a caldera system with abundant low-permeability layers of cemented breccia, provides a unique opportunity to study the influence of subsurface geological conditions on the hydrothermal fluid evolution. Coupled analyses of S isotopes performed in conjunction with Se and Fe isotopes have been applied for the first time to the study of seafloor hydrothermal systems. These data provide a tool for resolving the different abiotic and potential biotic near-surface hydrothermal reactions. The δ34S (between 1.5‰ and 4.6‰) and Se values (between 213 and 1640 ppm) of chalcopyrite suggest a high temperature end-member hydrothermal fluid with a dual source of sulfur: sulfur that was leached from basaltic rocks, and sulfur derived from the reduction of seawater sulfate. In contrast, pyrite and marcasite generally have lower δ34S within the range of magmatic values (0 ± 1‰) and are characterized by low concentrations of Se (<50 ppm). For 82Se/76Se ratios, the δ82Se values range from basaltic values of near −1.5‰ to −7‰. The large range and highly negative values of hydrothermal deposits observed cannot be explained by simple mixing between Se leached from igneous rock and Se derived from seawater. We interpret the Se isotope signature to be a result of leaching and mixing of a fractionated Se source located beneath hydrothermal chimneys in the hydrothermal fluid. At Lucky Strike we consider two sources for S and Se: (1) the “end-member” hydrothermal fluid with basaltic Se isotopic values (−1.5‰) and typical S isotope hydrothermal values of 1.5‰; (2) a fractionated source hosted in subsurface environment with negative δ34S values, probably from bacterial reduction of seawater sulfate and negative δ82Se values possibly derived from inorganic reduction of Se oxyanions. Fluid trapped in the subsurface environment is conductively cooled and has restricted mixing and provide favorable conditions for subsurface microbial activity which is potentially recorded by S isotopes. Fe isotope systematic reveals that Se-rich high temperature samples have δ57Fe values close to basaltic values (∼0‰) whereas Se-depleted samples precipitated at medium to low temperature are systematically lighter (δ57Fe values between −1 to −3‰). An important implication of our finding is that light Fe isotope composition down to −3.2‰ may be explained entirely by abiotic fractionation, in which a reservoir effect during sulfide precipitation was able to produce highly fractionated compositions.  相似文献   

9.
We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ13CCO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO2 concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ13CCO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ13C of the entire hydrothermal system, including mixed H2O-CO2 vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO2. On these grounds, we think that Mediterranean marine water (δDH2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO2 and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.  相似文献   

10.
The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the 238U/235U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed 236U-233U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ238U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ238U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ238U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ238U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ238U (−0.41‰ to −0.16‰) compared to seawater, which has δ238U of −0.41 ± 0.03‰. Granites define a range of δ238U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ238U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble UVI to insoluble UIV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that 238U/235U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in 207Pb/206Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.  相似文献   

11.
Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for 15N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu* anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ13C vs. δ15N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in 15N and 13C from a pristine source having δ13C ? −36‰ and δ15N ? −4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH4+(rock) and N2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large 13C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ15N value (+11‰), while C (up to 120 ppm and δ13C −38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The 15N-13C-depleted pristine source has δ 15N values from −7‰ to −4‰ and 40Ar/36Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and 40Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.  相似文献   

12.
Oxygen and iron isotope analyses of low-Ti and high-Ti mare basalts are presented to constrain their petrogenesis and to assess stable isotope variations within lunar mantle sources. An internally-consistent dataset of oxygen isotope compositions of mare basalts encompasses five types of low-Ti basalts from the Apollo 12 and 15 missions and eight types of high-Ti basalts from the Apollo 11 and 17 missions. High-precision whole-rock δ18O values (referenced to VSMOW) of low-Ti and high-Ti basalts correlate with major-element compositions (Mg#, TiO2, Al2O3). The observed oxygen isotope variations within low-Ti and high-Ti basalts are consistent with crystal fractionation and match the results of mass-balance models assuming equilibrium crystallization. Whole-rock δ56Fe values (referenced to IRMM-014) of high-Ti and low-Ti basalts range from 0.134‰ to 0.217‰ and 0.038‰ to 0.104‰, respectively. Iron isotope compositions of both low-Ti and high-Ti basalts do not correlate with indices of crystal fractionation, possibly owing to small mineral-melt iron fractionation factors anticipated under lunar reducing conditions.The δ18O and δ56Fe values of low-Ti and the least differentiated high-Ti mare basalts are negatively correlated, which reflects their different mantle source characteristics (e.g., the presence or absence of ilmenite). The average δ56Fe values of low-Ti basalts (0.073 ± 0.018‰, n = 8) and high-Ti basalts (0.191 ± 0.020‰, n = 7) may directly record that of their parent mantle sources. Oxygen isotope compositions of mantle sources of low-Ti and high-Ti basalts are calculated using existing models of lunar magma ocean crystallization and mixing, the estimated equilibrium mantle olivine δ18O value, and equilibrium oxygen-fractionation between olivine and other mineral phases. The differences between the calculated whole-rock δ18O values for source regions, 5.57‰ for low-Ti and 5.30‰ for high-Ti mare basalt mantle source regions, are solely a function of the assumed source mineralogy. The oxygen and iron isotope compositions of lunar upper mantle can be approximated using these mantle source values. The δ18O and δ56Fe values of the lunar upper mantle are estimated to be 5.5 ± 0.2‰ (2σ) and 0.085 ± 0.040‰ (2σ), respectively. The oxygen isotope composition of lunar upper mantle is identical to the current estimate of Earth’s upper mantle (5.5 ± 0.2‰), and the iron isotope composition of the lunar upper mantle overlaps within uncertainty of estimates for the terrestrial upper mantle (0.044 ± 0.030‰).  相似文献   

13.
Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with δD values from −64‰ to −25‰. All samples are enriched in water relative to fresh basalts. The δD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with δ13C values from −14.9‰ to −26.6‰. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with δ13C = −4.5‰ and (2) an organic compound with δ13C = −26.6‰. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when “fresh” oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ∼ −4.7‰, similar to the δ13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 × 1012 molC/yr.  相似文献   

14.
A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C1/C2+ > 100), high C2/C3 and i-C4/n-C4 ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ13CCH4 from −79.5‰ to −45.0‰, δ13CC2H6 from −53.7‰ to −32.2‰, δ13CC3H8 from −36.5‰ to −20.1‰, δ13CnC4H10 from −32.7‰ to −24.5‰, and δ13CCO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with 13C enriched methane and 13C depleted CO2, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, 13C enriched methane and variable δ13C of CO2, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with 13C depleted methane and 13C enriched CO2, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain 13C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.  相似文献   

15.
The isotopic compositions of commercially available herbicides were analyzed to determine their respective 15N, 13C and 37Cl signatures for the purposes of developing a discrete tool for tracing and identifying non-point source contaminants in agricultural watersheds. Findings demonstrate that of the agrochemicals evaluated, chlorine stable isotopes signatures range between δ37Cl = −4.55‰ and +3.40‰, whereas most naturally occurring chlorine stable isotopes signatures, including those of road salt, sewage sludge and fertilizers, vary in a narrow range about the Standard Mean Ocean Chloride (SMOC) between −2.00‰ and +1.00‰. Nitrogen stable isotope values varied widely from δ15N = −10.86‰ to +1.44‰ and carbon stable isotope analysis gave an observed range between δ13C = −37.13‰ and −21.35‰ for the entire suite of agro-chemicals analyzed. When nitrogen, carbon and chlorine stable isotope analyses were compared in a cross-correlation analysis, statistically independent isotopic signatures exist suggesting a new potential tracer tool for identifying herbicides in the environment.  相似文献   

16.
Graphite in deep crustal enderbitic (orthopyroxene + garnet + plagioclase + quartz) granulites (740°C, 8.9 kb) of Nilgiri hills, southern India were investigated for their spectroscopic and isotopic characteristics. Four types of graphite crystals were identified. The first type (GrI), which is interstitial to other mineral grains, can be grouped into two subtypes, GrIA and GrIB. GrIA is either irregular in shape or deformed, and rough textured with average δ13C values of −12.7 ± 0.4‰ (n = 3). A later generation of interstitial graphite (GrIB) shows polygonal crystal shapes and highly reflecting smooth surface features. These graphite grains are more common and have δ13C values of −11.9 ± 0.3‰ (n = 14). Both subtypes show well-defined Raman shifts suggesting a highly crystalline nature. Cores of interstitial graphite grains have, on average, lower δ13C values by ∼0.5‰ compared to that of the rim. The second type of graphite (GrII) occurs as solid inclusions in silicate minerals, commonly forming regular hexagonal crystals with a slightly disordered structure. The third type of graphite (GrIII) is associated with solid inclusions (up to 100 μm) that have decrepitation halos of numerous small (<15 μm) satellite fluid inclusions of pure CO2 with varying density (1.105 to 0.75 g/cm3). The fourth type of graphite (GrIV) is found as daughter crystals within primary type CO2-fluid inclusions in garnet and quartz. These fluid inclusions have a range of densities (1.05 to 0.90 g/cm3), but in general are significantly less dense than graphite-free primary, pure CO2 fluid inclusions (1.12 g/cm3). Raman spectral characteristics of graphite inside fluid inclusions suggest graphite crystallization at low temperature (∼ 500°C). The precipitation of graphite probably occurred during the isobaric cooling of CO2-rich peak metamorphic fluid as a result of oxyexsolution of oxide phases. The oxyexsolution process is evidenced by the magnetite-ilmenite granular exsolution textures and the systematic presence of numerous micron-sized rutile and other oxide inclusions in association with fluid inclusions within garnet, plagioclase, and quartz.The carbon isotope compositions of coexisting CO2 (in fluid inclusions) and graphite show a fractionation (α2CO−gr) of ∼6‰ in garnet, consistent with the existing theoretical estimates of α2CO−gr at 800°C. A subsequent generation of CO2 inclusions trapped in matrix quartz and quartz segregation have higher δ13C values, −4‰ and −2.9‰ respectively. Graphite in quartz segregations also has higher δ13C values (−9.8‰) than those in enderbite (−12.7‰). Micro-graphite crystals included in garnet, quartz (enderbite), and quartz (segregation) have average δ13C values of −11.1, −10.4, and −8.7‰ respectively, indicating progressive enrichment in 13C with a decrease in temperature of recrystallization of respective minerals. This progressive enrichment is also observed in carbon isotope compositions of fluid inclusion CO2, suggesting isotopic equilibrium during graphite precipitation from CO2 fluids. Thus, the carbon isotope record preserved in these rocks by the interstitial graphite, CO2 fluid in enderbite, graphite microcrystals, graphite in quartz segregation, and CO2 fluid in quartz segregation, suggests a temperature-controlled isotopic evolution. This evolution is in accordance with a closed system Rayleigh-type graphite precipitation process which progressively enriched residual CO2 in 13C.  相似文献   

17.
In the Schwarzwald area, southwest Germany, more than 400 hydrothermal veins hosting different gangue and ore mineral assemblages cross-cut the crystalline basement rocks. Many of the post-Variscan fluorite-barite-quartz veins are considered to have precipitated through mixing of a deep saline brine with meteoric, low salinity waters. This hypothesis was tested using carbon, sulfur, and oxygen isotope data of sulfides, sulfates and calcite, coupled with fluid inclusion studies. Primary hydrothermal calcites from the deposits show a positive correlation of their δ13C (V-PDB) and δ18O (V-SMOW) values, which range from −12 to −3‰ and from 12 to 18.5‰, respectively. Carbon and oxygen isotope compositions of paragenetically young, remobilized calcite types are shifted towards higher values and range from −12 to −1‰ and from 20 to 25‰, respectively. We developed an improved calculation procedure for modeling the covariation of carbon and oxygen isotopes in calcite resulting from mixing of two fluids with different isotopic compositions and total carbon concentrations. In our model, the carbon speciation in the two model fluid end-members and the fluid mixtures are calculated using a speciation and reaction path code. The carbon and oxygen isotope covariation of primary Schwarzwald calcites can effectively be modeled by a mixing trend of a deep saline brine and a meteoric, low salinity water. Sulfur isotope data of barites from 44 hydrothermal fluorite-barite-quartz veins vary from 9 to 18‰ (CDT), sulfide ore minerals show δ34S values between −14.4 and 2.9‰. Calculated sulfide-sulfate equilibrium temperatures are in the range between 300 and 350 °C. These temperatures differ significantly from the formation temperatures of 150 to 200 °C of most of the deposits as estimated from fluid inclusions, and are interpreted as preserved paleotemperatures of the deep aquifer. This assumption has been carefully checked against possible contamination of an equilibrated sulfide-sulfate system from the deep aquifer with sulfate from surface-derived sources, considering also the kinetics of the sulfide-sulfate isotope exchange. A combination of the S isotopic results with microthermometric fluid inclusion data and constraints on the temperature of the meteoric water was used to calculate mixing ratios of the two fluid end-members. The results indicate that mass fractions of the deep saline brine in the mixed fluid were between 0.5 and 0.75. Considering all geologic, geochemical and isotopic information, we propose that the majority of the post-Variscan hydrothermal veins in the Schwarzwald area were precipitated by district-scale mixing of a homogeneous deep saline brine with meteoric waters.  相似文献   

18.
Active and inactive carbonate chimneys from the Lost City Hydrothermal Field contain up to 0.6% organic carbon with diverse lipid assemblages. The δ13C values of total organic carbon range from −21.5‰ vs. VPDB at an extinct carbonate chimney to −2.8‰ at a 70 °C, actively venting carbonate chimney. Samples collected at locations with total organic carbon with δ13C > −15‰ also contained high abundances of isoprenoidal and nonisoprenoidal diether lipids. Samples with TOC more depleted in 13C lacked or contained lower amounts of these diethers.Isoprenoidal diethers, including sn-2 hydroxyarchaeol, sn-3 hydroxyarchaeol, and putative dihydroxyarchaeol, are likely to derive from methanogenic archaea. These compounds have δ13C values ranging from −2.9 to +6.7‰ vs. VPDB. Nonisoprenoidal diethers and monoethers are presumably derived from bacteria, and have structures similar to those produced by sulfate-reducing bacteria in culture and at cold seeps. In samples that also contained abundant hydroxyarchaeols, these diethers have δ13C values between −11.8 and +3.6‰. In samples without abundant hydroxyarchaeols, the nonisoprenoidal diethers were typically more depleted in 13C, with δ13C as low as −28.7‰ in chimneys and −45‰ in fissures.The diethers at Lost City are probably derived from hydrogen-consuming methanogens and bacteria. High hydrogen concentrations favor methanogenesis over methanotrophy and allow the concurrent growth of methanogens and sulfate-reducing bacteria. The unusual enrichment of 13C in lipids can be attributed to nearly complete consumption of bioavailable carbon in vent fluids. Under carbon-limited conditions, the isotope effects that usually lead to 13C-depletion in organic material cannot be expressed. Consequently, metabolic products such as lipids and methane have δ13C values typical of abiotic carbon.  相似文献   

19.
Li isotope fractionation in peridotites and mafic melts   总被引：4，自引：0，他引：4  
We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of 7Li/6Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ7Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ7Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ7Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ7Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ7Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ7Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.  相似文献   

20.
The Western Slope of the Songliao Basin is rich in heavy oil resources (>70 × 108 bbl), around which there are shallow gas reservoirs (∼1.0 × 1012 m3). The gas is dominated by methane with a dryness over 0.99, and the non-hydrocarbon component being overwelmingly nitrogen. Carbon isotope composition of methane and its homologs is depleted in 13C, with δ13C1 values being in the range of −55‰ to −75‰, δ13C2 being in the range of −40‰ to −53‰ and δ13C3 being in the range of −30‰ to −42‰, respectively. These values differ significantly from those solution gases source in the Daqing oilfield. This study concludes that heavy oils along the Western Slope were derived from mature source rocks in the Qijia-Gulong Depression, that were biodegraded. The low reservoir temperature (30–50 °C) and low salinity of formation water with neutral to alkaline pH (NaHCO3) appeared ideal for microbial activity and thus biodegradation. Natural gas along the Western Slope appears mainly to have originated from biodegradation and the formation of heavy oil. This origin is suggested by the heavy δ13C of CO2 (−18.78‰ to 0.95‰) which suggests that the methane was produced via fermentation as the terminal decomposition stage of the oil.  相似文献   

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