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1.
The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids, molluscan mold-fill and sparry pore-fill calcite cements are depleted in 18O and 13C compared to those of contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis. Based on δ13C and δ18O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric diagenetic realm (δ13C from −7.8‰ to −6.0‰ and −9.0‰ to −7.0‰; δ18O from −9.2‰ to −6.5‰ and −9.4‰ to −2.6‰, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water recharge zone. The negative δ18O values of various carbonate components (about −9.4‰ to −4.1‰ for whole rocks; about −8.4‰ to −2.6‰ for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid, unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (−7.9‰ to −3.6‰ for whole rocks; −4.9‰ to −1.5‰ for ooids) are consistent with the interpretation that the paleo-ecosystem comprised a significant proportion of C4 type plants, supporting a scenario of expansion of C4 plants during the late Miocene in the Indian subcontinent as far south as the southern tip of India. The 87Sr/86Sr ratios of the Kudankulam carbonates (0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and 0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic 87Sr influx to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were already exposed in southern India by the late Miocene.  相似文献   

2.
The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ18O) in 61 subsamples (along three branches of a single unaltered colony) range from −0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ13C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ18O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ18O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ18O and 1.34 in δ13C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.  相似文献   

3.
Three categories of fibrous calcite from early to middle Caradoc platform-marginal buildups in east Tennessee can be delineated using cathodoluminescent microscopy, minor element chemistry and stable C-O isotopic composition. Bright luminescent fibrous cement has elevated Mn (>1000 p.p.m.), negative δ13C and intermediate δ18O values relative to other types of fibrous calcite. This cement reflects fibrous calcite that interacted with reducing Mn-rich fluids. Dully luminescent fibrous cement has elevated Fe (>400 p.p.m.), positive δ13C and negative δ18O values relative to other fibrous cements. This cement was stabilized by burial fluids. Nonluminescent fibrous cement has low Mn and Fe (generally below 400 p.p.m.) and positive δ13C and δ18O values relative to other types of fibrous calcite. The latter cement is interpreted to be the best material for determining the isotopic composition of calcite precipitated in equilibrium with early to middle Caradoc seawater, which is δ13C=1% PDB and δ18O=?4 to ?5‰ PDB. Results from this study and Ashgillian brachiopods indicate that the average δ18O composition of the Ordovician ocean, during nonglacial periods, was probably never more negative than ?3‰ SMOW. Assuming an Ordovician seawater δ18O value of ?1‰ SMOW, Holston Formation fibrous cements would have precipitated at temperatures between 27 and 36 °C, which is near the upper temperature limit for metazoans. A seawater δ18O value of ?2‰ SMOW yields temperatures ranging from 23 to 31 °C, while a ?3‰ SMOW value yields temperatures of 18–26 °C.  相似文献   

4.
Coupled records of Sr/Ca and oxygen isotope ratios (δ18O) of coral skeletons have been used to produce quantitative estimates of paleo-sea surface temperature (SST) and δ18O of surface seawater that can in some cases be converted to sea surface salinity (SSS). Two fossil corals from Kikai Island in the subtropical northwestern Pacific, a location affected by East Asian summer and winter monsoons, were analyzed to investigate differences between mid-Holocene and present-day SST and SSS. At 6180 cal yr BP, SSTs were roughly the same as today, both in summer and winter; δ18Oseawater and SSS values were higher both in summer (+ 0.5‰, +1.1 psu) and in winter (+ 0.2‰, + 0.6 psu) than modern values. At 7010 cal yr BP, SSTs were slightly cooler both in summer and winter (−0.8 and −0.6 °C), whereas δ18Oseawater and SSS had higher values in summer (+ 0.3‰, + 0.6 psu) and in winter (+ 0.8‰, + 1.9 psu) than present-day values. These results are consistent with other marine records for the mid-Holocene of the low and midlatitudes in the northwestern Pacific. Such regional conditions indicate that the East Asian summer and winter monsoons were more intense in the mid-Holocene, which was likely a function of the mid-Holocene insolation regime.  相似文献   

5.
The Gordon Group carbonates consist of biota of the Chlorozoan assemblage, diverse non‐skeletal grains and abundant micrite and dolomite, similar to those of modern warm water carbonates. Cathodoluminescence studies indicate marine, meteoric and some burial cements. Dolomites replacing burrows, mudcracks and micrite formed during early diagenesis.

δ18O values (‐5 to ‐7%ō PDB) of the non‐luminescent fauna and marine cement are lighter than those of modern counterparts but are similar to those existing within low latitudes during the Ordovician because of the light δ18O values of Ordovician seawater (‐3 to ‐5%o SMOW). The δ18O difference (2%o) between marine and meteoric calcite indicates that Ordovician meteoric water was similar to that in modern subtropics. Values of δ13C relative to δ18O indicate that during the Early Ordovician there were higher atmospheric CO2 levels than at present but during the Middle and Late Ordovician they became comparable with the present because of a change from ‘Greenhouse’ to glacial conditions. δ18O values of Late Ordovician seawater were heavier than in the Middle Ordovician mainly because of glaciation.

Dolomitization took place in marine to mixed‐marine waters while the original calcium carbonate was undergoing marine to meteoric diagenesis.  相似文献   

6.
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   

7.
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   

8.
We report a study of the oxygen isotope ratios of chondrules and their constituent mineral grains from the Mokoia, oxidized CV3 chondrite. Bulk oxygen isotope ratios of 23 individual chondrules were determined by laser ablation fluorination, and oxygen isotope ratios of individual grains, mostly olivine, were obtained in situ on polished mounts using secondary ion mass spectrometry (SIMS). Our results can be compared with data obtained previously for the oxidized CV3 chondrite, Allende. Bulk oxygen isotope ratios of Mokoia chondrules form an array on an oxygen three-isotope plot that is subparallel to, and slightly displaced from, the CCAM (carbonaceous chondrite anhydrous minerals) line. The best-fit line for all CV3 chondrite chondrules has a slope of 0.99, and is displaced significantly (by δ17O ∼ −2.5‰) from the Young and Russell slope-one line for unaltered calcium-aluminum-rich inclusion (CAI) minerals. Oxygen isotope ratios of many bulk CAIs also lie on the CV-chondrule line, which is the most relevant oxygen isotope array for most CV chondrite components. Bulk oxygen isotope ratios of most chondrules in Mokoia have δ18O values around 0‰, and olivine grains in these chondrules have similar oxygen isotope ratios to their bulk values. In general, it appears that chondrule mesostases have higher δ18O values than olivines in the same chondrules. Our bulk chondrule data spread to lower δ18O values than any ferromagnesian chondrules that have been measured previously. Two chondrules with the lowest bulk δ18O values (−7.5‰ and −11.7‰) contain olivine grains that display an extremely wide range of oxygen isotope ratios, down to δ17O, δ18O around -50‰ in one chondrule. In these chondrules, there are no apparent relict grains, and essentially no relationships between olivine compositions, which are homogeneous, and oxygen isotopic compositions of individual grains. Heterogeneity of oxygen isotope ratios within these chondrules may be the result of incorporation of relict grains from objects such as amoeboid olivine aggregates, followed by solid-state chemical diffusion without concomitant oxygen equilibration. Alternatively, oxygen isotope exchange between an 16O-rich precursor and an 16O-poor gas may have taken place during chondrule formation, and these chondrules may represent partially equilibrated systems in which isotopic heterogeneities became frozen into the crystallizing olivine grains. If this is the case, we can infer that the earliest nebular solids from which chondrules formed had δ17O and δ18O values around -50‰, similar to those observed in refractory inclusions.  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.
Unusual 18O depletion, with δ18O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ18O zircons to be distinguished between magmatic and metamorphic origins, because the 18O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ18O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual 18O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ18O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ18O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ18O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ18O zircons are interpreted as crystallizing from negative δ18O magmas due to melting of meteoric-hydrothermally altered negative δ18O rocks in an active rift setting at about 780 Ma. The variation in zircon δ18O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive εHf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ18O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ18O zircons may register centers of low δ18O magmatism during the supercontinental rifting.  相似文献   

11.
A total of 280 brachiopods of Ordovician to Cretaceous age, complemented by published data from belemnites and planktonic foraminifera, are used to reconstruct the evolution of calcium isotope composition of seawater (δ44/40CaSW) over the Phanerozoic. The compiled δ44/40CaSW record shows a general increase from ∼1.3‰ (NIST SRM 915a) at the beginning of the Ordovician to ∼2‰ at present. Superimposed on this trend is a major long-term positive excursion from the Early Carboniferous to Early Permian as well as several short-term, mostly negative, oscillations.A numerical model of the global cycles of calcium, carbon, magnesium and strontium was used to estimate whether the recorded δ44/40CaSW variations can be explained by varying magnitudes of input and output fluxes of calcium to the oceans. The model uses the record of marine 87Sr/86Sr ratios as proxy for seafloor spreading rates, a record of oceanic Mg/Ca ratios to estimate rates of dolomite formation, and reconstructed atmospheric CO2, discharge and erosion rates to estimate continental weathering fluxes.The model results indicate that varying magnitudes of the calcium input and output fluxes cannot explain the observed δ44/40CaSW trends, suggesting that the isotope signatures of these fluxes must also have changed. As a possible mechanism we suggest variable isotope fractionation in the sedimentary output flux controlled by the dominant mineralogy in marine carbonate deposits, i.e. the oscillating ‘calcite-aragonite seas’. The ultimate control of the calcium isotope budget of the Phanerozoic oceans appears to have been tectonic processes, specifically variable rates of oceanic crust production that modulated the hydrothermal calcium flux and the oceanic Mg/Ca ratio, which in turn controlled the dominant mineralogy of marine carbonates, hence the δ44/40CaSW. As to the causes of the short-term oscillations recorded in the secular δ44/40CaSW trend, we tentatively propose that these are related to variable rates of dolomite formation and/or to changing chemical composition of the riverine flux, in particular and ratios, induced by variable proportions of silicate vs. carbonate weathering rates on the continents.  相似文献   

12.
A complex history of diagenetic interactions between a siliceous sediment, seawater and fresh water is revealed by intraformational chert breccias. Chert breccias were formed in the Campanian Mishash Formation in Israel, by “practically contemporaneous” fracturing of lithified cherty layers followed by silicification and lithification of the matrix. Pairs of fragments and matrix were compared with respect to their chemical (Ca, Sr, Na, K, Mg, Li, B, SO4, Ba) and isotopic (δ18O, δD, δ11B) composition. δ11B was analyzed by ion-probe and includes a profile across a fragment-matrix contact. The epicontinental cherts of the Mishash Fm. are enriched by a factor of 10 to 50 in all elements other than O and Si in comparison with Deep-Sea cherts. All results are compatible with the proposition that the lithification of the matrix occurred in contact with fresh-water, as opposed to seawater in which the fragments, as well as most of the Mishash sediments were formed. The strongest evidence for this difference is in the higher concentration of B in the fragments (27-70 ppm vs. 11-21ppm in the matrix) and higher δ18O (29 to 35‰ vs. 21 to 33‰). δD is a less efficient discriminator, though compatible with fresher water diagenesis of the matrix: −115‰ to −76‰ for hydrogen in the chert of the fragments, compared to −141 to −85‰ for the matrix. δ11B in the matrix shows some of the lowest values recorded in sediments (δ11B = −33‰), but varies strongly, suggesting that the source of boron in the matrix is a mixture of a freshwater and a marine component. Both seawater and the freshwater that has equilibrated with the cherts underwent varying degrees of evaporation. Ca, Sr and SO4 are carried by apatite, trapped as detritus in the matrix. The concentration of lithium in the matrix is high (11-16 ppm), whereas in the adjacent fragments it is mostly only within 1-2 ppm. Li probably enters the matrix from the interstitial solution, during the opal → quartz transformation. The second, prolonged, transformation takes place in a (freshwater) flow-through, open system. This allows a much larger mass of Li to be scavenged by the transforming silica despite its low concentration in freshwater.  相似文献   

13.
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   

14.
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   

15.
The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ18O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ18O of surface water. The following trends and patterns are recognized within this range of δ18O values. First, in Cenozoic rocks of northern Nevada, chert δ18O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ18O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ18O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ18O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ18O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.  相似文献   

16.
Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ7Li, δ11B, 87Sr/86Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ7Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ7Li values (+1.4%), the other geothermal waters have a near constant δ7Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ11B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The 87Sr/86Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand.  相似文献   

17.
Carbonate δ13C values provide a useful monitor of changes in the global carbon cycle because they can record the burial ratio of organic to carbonate carbon. The most pronounced isotope excursions in the geologic record occur during the Neoproterozoic and have assumed a central role in the interpretation of biogeochemical events preceding the Ediacaran and Cambrian radiations. The most profound negative carbon isotope excursion is best recorded in the Ediacaran-aged Shuram Formation of Oman and has potential equivalents worldwide including the Wonoka Formation of South Australia and other sections in China, India, Siberia, Canada, Scandinavia and Brazil. All these excursions are less well understood than those in the Phanerozoic because of their unusual magnitude, long duration (> 1 Ma) and the difficulty in correlating Neoproterozoic basins to confirm independently that they do indeed record global change in the mixed ocean reservoir. Alternatively, these δ13C anomalies could reflect diachronous diagenetic processes. Currently none of these excursion are firmly time constrained and critical to their interpretation is a coherent reproducibility and synchroneity at the global ocean scale. Here we use available strontium isotope record as an independent chronometer to test the timing and synchroneity of the Shuram δ13C and its potential equivalents. The use of the 86Sr/87Sr ratio allows the reconstruction of a coherent, global δ13C record calibrated independently against time. The calibrated δ13C curve indicates that the Shuram negative anomaly spans several tens of millions of years and reaches values below −10‰. This carbon isotopic anomaly therefore represents a meaningful oceanographic event that fundamentally challenges our understanding of the carbon cycle as defined in the Phanerozoic.  相似文献   

18.
The stable isotope composition (δ15N and δ18O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ15N and δ18O values for residual nitrate. Maximum δ15N and δ18O values amounted to 27.2 and 15.7‰, respectively.15N and 18O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ18O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ15N.  相似文献   

19.
A large collection of fluids (54 interstitial fluids and four expelled fluids) were sampled at the Manon site, at the outer edge of the Barbados accretionary complex. These warm fluids (up to 20°C) are expelled by sub-marine (5000 mbsl) mud volcanoes consisting of diapirs (unchanneled flow) and diatremes (channeled).Chlorine stable isotope ratios of these fluids were measured by IRMS with a reproducibility of ± 0.05‰ (1σ) versus SMOC (Standard Mean Ocean Chloride).A large range of δ37Cl between −5.3‰ and +0.1‰ is observed. Data from each volcanic structure describe a mixing between seawater and a low-δ37Cl fluid. The whole set of data is interpreted as the result of a mixing between two deep components and seawater. The two deep fluids are chemically distinct (e.g., in Ca, Mg, K, Li, Sr and Br contents and Br/Cl ratio). They display low and significantly different 87Sr/86Sr ratios (0.707790 and 0.707892, respectively) and δ37Cl values (−4.51 and −5.24‰, respectively).Physicochemical processes such as mineralogical transformation, diffusion, compaction or ion filtration are known to fractionate chlorine stable isotopes and can produce fluids with negative δ37Cl values. Ion filtration due to sediment compaction appears to be the more likely process to explain the negative δ37Cl values observed at the Manon site. A model for the generation of these signatures is proposed where a residual negative δ37Cl fluid reservoir is created at the bottom of the prism or the sediment pile. Further compaction/fracturing and/or dewatering of the slab may flush out these fluids and focus them towards the décollement zone. Mixing between the fluids and ultimately with seawater and water released during gas hydrate destabilizations may explain the data set within the individual cores and between the different structures.  相似文献   

20.
The Yurungkash and Karakash rivers, also known respectively as the White Jade and Black Jade rivers, located in Hetian, Xinjiang Province, Northwest China, are the two main sources in China of white, green, and black placer nephrite, with a long history (~ 5000 years) of exploration and mining. The twenty-nine placer nephrite samples collected from both rivers and analyzed in the present study possess fine-grained and compact microstructures. The mineral assemblages in the samples provide clues to the metamorphic/metasomatic processes that formed the nephrite, which was the result of one of the following reactions: dolomitic marble → tremolite, or dolomitic marble → diopside → tremolite. White nephrite from the Yurungkash River and green nephrite from the Karakash River are predominantly tremolite. Based on electron probe microanalytical data, backscattered electron images, and Raman spectra, two kinds of black nephrite from the Karakash River are identified: one dominated by actinolite aggregates, and another consisting of tremolite aggregates with graphite crystals up to 2 mm in length. Compared with black nephrite, white and green nephrites contain fewer mineral inclusions and have lower FeO and MnO contents. All the amphiboles in the nephrites have very low contents of Cr2O3 (0.00–0.07 wt.%) and NiO (0.00–0.05 wt.%) relative to serpentinite-related nephrite (0.07–0.43 wt.% Cr2O3, 0.08–0.36 wt.% NiO). Most of the nephrite samples have low total rare earth element (ΣREE) contents, ranging from 12.22 to 49.40 ppm. In two nephrite samples, relatively high ΣREE concentrations (161 and 190 ppm) are related to the presence of REE-bearing minerals. Whole-rock REE chondrite-normalized patterns of all samples are characterized by strong negative Eu anomalies (0.16–0.48), moderate light-REE enrichment (La/NdN = 1.8–5.0), and nearly flat heavy-REE distributions (Gd/YbN = 0.3–1.7). Nephrite samples from both river locations have δ18O and δD isotope compositions ranging from 1.1‰ to 5.6‰ and − 55.7‰ to − 72.4‰, respectively. These values are closer to those recorded in dolomite-related nephrites than those in serpentinite-related deposits. Importantly, δ18O and δD values correspond to fluid isotope compositions of δ18O = 1.6‰ to 6.1‰ (330 °C), 1.8‰ to 6.3‰ (350 °C), and 2.5‰ to 7.0‰ (430 °C), and δD = − 34.9‰ to − 52.5‰ (350 °C to 650 °C). These values are close to or within the field of magmatic water. Geochemical and petrographic characteristics point to a dolomite-related metamorphic/metasomatic origin for nephrite at both locations. The placer nephrite is likely to have been derived from primary nephrite deposits in the Kunlun Mountains around Hetian, based on the geological occurrence of the deposits.  相似文献   

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