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1.
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   

2.
为了进一步理解华南下寒武统Ni-Mo-Se多金属层的物质来源及形成环境,文中分析了遵义中南村和张家界后坪两个Ni-Mo-Se矿层及其围岩的黄铁矿硫同位素和全岩的硒同位素组成。硫同位素组成显示两个Ni-Mo-Se矿层形成时的环境存在区域性差别,中南村矿层形成于间歇开放的海洋环境,而后坪矿层形成于封闭的缺氧(静海)环境。较大的硫同位素范围暗示硫酸盐还原菌控制硫同位素的分馏,而热液流体可能提供了大量金属元素,从而导致矿层富集大量的硫化物和稀有金属。硒同位素组成指示牛蹄塘组底部热液流体的Se可能重新经历了氧化还原循环,而Se的富集过程可能受有机质和粘土矿物吸附或类质同象过程控制。因此,控制多金属富集的因素主要为富集金属的热液流体的参与和缺氧环境下的自生沉积。  相似文献   

3.
Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ34S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ34S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ18O values, have elevated δ34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ34S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).  相似文献   

4.
The Li isotopic composition of the upper continental crust is estimated from the analyses of well-characterized shales, loess, granites and upper crustal composites (51 samples in total) from North America, China, Europe, Australia and New Zealand. Correlations between Li, δ7Li, and chemical weathering (as measured by the Chemical Index of Alteration (CIA)), and δ7Li and the clay content of shales (as measured by Al2O3/SiO2), reflect uptake of heavy Li from the hydrosphere by clays. S-type granites from the Lachlan fold belt (-1.1 to -1.4‰) have δ7Li indistinguishable from their associated sedimentary rocks (-0.7 to 1.2‰), and show no variation in δ7Li throughout the differentiation sequence, suggesting that isotopic fractionation during crustal anatexis and subsequent differentiation is less than analytical uncertainty (±1‰, 2σ). The isotopically light compositions for both I- and S-type granites from the Lachlan fold belt (-2.5 to + 2.7 ‰) and loess from around the world (-3.1 to + 4.5‰) reflect the influence of weathering in their source regions. Collectively, these lithologies possess a limited range of Li isotopic compositions (δ7Li of −5‰ to + 5‰), with an average (δ7Li of 0 ± 2‰ at 1σ) that is representative of the average upper continental crust. Thus, the Li isotopic composition of the upper continental crust is lighter than the average upper mantle (δ7Li of + 4 ± 2‰), reflecting the influence of weathering on the upper crustal composition. The concentration of Li in the upper continental crust is estimated to be 35 ± 11 ppm (2σ), based on the average loess composition and correlations between insoluble elements (Ti, Nb, Ta, Ga and Al2O3, Th and HREE) and Li in shales. This value is somewhat higher than previous estimates (∼20 ppm), but is probably indistinguishable when uncertainties in the latter are accounted for.  相似文献   

5.
In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH4 (0.01–50.55 mol%) with low δ13C–CH4 values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ13C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH4 to ethane and propane ratios (3–35 mol%; C1/C2 + C3) and high δ13C and δD values of CH4 (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH4 was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ13C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO4 values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ13C–DIC values (<−22‰) and relatively high SO4 concentrations (up to 12.31 mmole/L) in many brine samples point to SO4 reduction, which likely limits microbial CH4 generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH4 in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH4 are present at shallow depths along Lake Erie and in western NY.  相似文献   

6.
Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ18OVSMOW and δ2HVSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ18OVSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ18OVSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ13CVPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO2 and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ13CVPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ13CVPDB), indicating carbon isotopic fractionation from methanogenesis via CO2 reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH4-degassing during sampling.  相似文献   

7.
We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ56Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ26Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ56Fe; ±0.10‰ for δ26Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ56Feol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ56Feol-opx = −0.05 ± 0.11‰; Δ26Mgol-opx = −0.09 ± 0.12‰; Δ26Mgol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ56Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ26Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ56Fe and δ26Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ56Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ56Fe, the larger deviations from average δ56Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ56Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ56Fe and slightly heavy δ26Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.  相似文献   

8.
The stable nitrogen isotopic composition of nitrate, concentrations of inorganic nitrogen and phosphorus, dissolved oxygen and nitrification rates were determined at six stations ranging from the oligotrophic North Pacific Subtropical Gyre (NPSG) to the more productive Eastern Tropical North Pacific (ETNP). Nitrification rates increased along the transect from a maximum rate of 1 nmol L−1 d−1 at station ALOHA to 23.7 nmol L−1 d−1 at station 6. In oxic surface waters, nitrate isotopically enriched in 15N (maximum δ15N-NO3− value of 12.5‰) was most likely the result of assimilatory nitrate reduction. In contrast, high δ15N-NO3− values (maximum of 12.3‰) in association with high nitrate deficits and anoxic conditions supported the interpretation of isotopic fractionation due to denitrification. A one-dimensional vertical advection and diffusion model was used to estimate the fractionation factor for denitrification at two stations in the ETNP. A comparison of modeled to observed δ15N-NO3− data indicated an isotopic enrichment factor (ε) of 30‰ at station 4 and 30 to 35‰ at station 5. Isotopically light nitrate (1.1 and 3.2‰) was observed in the upper 200 m of the water column at stations in the ETNP. Tracer studies of 15NH4 and biogeochemical indicators of nitrogen fixation supported the interpretation of nitrification as the most plausible explanation for low δ15N-NO3− values observed in water column samples. Our results are consistent with the occurrence of nitrification within the euphotic zone and for the first time provide corroborating stable nitrogen isotopic evidence for this process.  相似文献   

9.
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   

10.
Ultramafic rocks of the Duke Island Complex in southeastern Alaska crystallized in a supra-subduction zone setting, but the serpentinization of olivine-bearing rocks involved the incursion of late-stage meteoric waters. Three textural types of serpentine (primarily lizardite) have been identified which in part reflect progress in reactions during multiple stages of fluid infiltration. The overall mesh texture of serpentine has been subdivided into a massive-type, found in dunites and wehrlites, and a dendritic-type found in wehrlites and olivine clinopyroxenites. Serpentine veins represent a late-stage in the hydrothermal alteration process. Both FeO contents and δ18O values of the three textural types of serpentine are variable at the centimeter scale. Magnetite abundance in association with serpentine is also variable with up to 5 vol% of magnetite found in samples with dendritic serpentine. Continued reaction of FeO-bearing serpentine with fluid appears to control the formation of most magnetite. Oxygen isotope ratios of the three textural types of serpentine are distinct, with the massive variety characterized by δ18O values between −3‰ and 3‰, the dendritic variety showing values between 2‰ and 6‰ and the veins having the highest values between 4‰ and 10‰. Although the δ18O values may vary by as much as 5‰ on the centimeter scale, δD values tend to show relatively less variation with over 90% of the measured values between −100‰ and −120‰. The O and H isotopic values are consistent with the involvement of meteoric water that had undergone variable degrees of isotopic exchange with country rocks prior to reacting with olivine in the Duke Island Complex. Small-scale variability in both serpentine FeO content and δ18O values suggests that chemical and isotopic equilibria may have not been attained at larger than centimeter scales. Oxygen isotopic variability in serpentine produced during relatively low-temperature hydrothermal alteration is in large part a function of exchange mediated via fluid flow through microfractures.  相似文献   

11.
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   

12.
The formation of authigenic Ca-rich rhodochrosite (ACR) in sapropelic sediments of the Gotland Basin, Baltic Sea, is governed by deepwater renewal processes whereby saline water from the North Atlantic flushes the brackish anoxic Baltic Deeps. The carbon and oxygen isotopic compositions of these Mn-carbonates suggest that ACR formation takes place just below the sediment surface and that dissolved compounds from the deepwater column, such as water and bicarbonate molecules, were incorporated in ACR during authigenesis. Porewaters near the sediment surface display δ18O values of −5.4‰ (VSMOW) and are generally depleted in 18O, compared to the oxygen isotopic composition of water in equilibrium with Mn-carbonate solid solutions (ACR δ18O values are −4.6‰). This suggests that early burial diagenetic processes significantly modify the initial isotopic composition of water during Mn-carbonate formation. The reduction of sulfate having δ18O values of +8.4‰ accounts for a permanent enrichment of porewater 18O and observed δ18O values at depth equal to −4.6‰. However, this process does not explain the observed disequilibrium in the oxygen isotopic composition between water and ACR close to the sediment surface where Mn-carbonate formation takes place. Based on isotopic mass balance calculations, we suggest that MnO2 with δ18O values of +8.9‰ released oxygen enriched in 18O into the anoxic porewaters close below the sediment surface. This process should occur after oxygenation events during deepwater renewal when MnO2 accumulates at the surface of anoxic sediments. Manganese carbonates formed in these waters display δ18O values of ∼1.0‰ heavier than values expected solely from the initial deepwater composition. This quantitatively explains the discrepancy between paleosalinities calculated from ACR δ18O based on Mn-carbonate/water isotopic equilibrium fractionation and direct observations for the same period. Our results emphasize the important role of microbial MnO2 reduction during rhodochrosite authigenesis and suggest that Mn(II) activity, rather than alkalinity, is the limiting component for sedimentary Mn-carbonate formation.  相似文献   

13.
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   

14.
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   

15.
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   

16.
Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in δ56Fe (differences in the 56Fe/54Fe ratio relative to the IRMM-14 standard) from −0.27 ± 0.09‰ to +0.21 ± 0.08‰. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean δ56Fe of +0.08 ± 0.13‰, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean δ56Fe of −0.14 ± 0.19‰. Negative correlations of the δ56Fe values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of −1.06 ± 0.20‰ for δ56Fe. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved δ56Fe value of about −1.4‰ to −0.9‰. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive δ56Fe values.  相似文献   

17.
Sulfur isotopic compositions were determined by ion microprobe for 36 spots on anhydrite crystals in trachyandesitic pumices erupted from El Chichón Volcano in 1982. Individual anhydrite crystals are homogeneous in δ34S, within the ±1‰ (2σ) uncertainty of the method, but crystal-to-crystal variations are large (+2.5 to +10.9‰). The mean δ34S for anhydrite (+6.4 ± 2.1‰, 1σ) is significantly lower than earlier results for bulk anhydrite separates (+9.0 to +9.2‰). The difference between the mean δ34S values in these two populations may reflect a grain-size effect, with heavier sulfur concentrated in smaller anhydrite crystals, few of which were analyzed by ion microprobe. Variations in δ34S show no correlation with complex textures in anhydrite revealed by cathodoluminescence color. Ion-microprobe analyses of δ34S were also obtained on six ovoid-shaped inclusions of pyrrhotite, chalcopyrite, and/or intermediate sulfide solid solution hosted by silicate or oxide crystals, interpreted to be magmatic (δ34S = −0.1 to +2.7‰; mean +0.7‰), and on four irregularly shaped multiphase sulfide fragments in the matrix, interpreted as xenocrystic, which range widely in δ34S (−3.7 to +5.5‰). We evaluate four different mixing scenarios involving (1) magmatic anhydrite and sedimentary sulfate, (2) magmatic anhydrite and hydrothermal anhydrite, and anhydrite and coexisting sulfide crystals precipitated in different domains of a common magma reservoir that were affected by (3) different degrees of degassing or (4) different degrees of crustal sulfur contamination. The model involving physical contamination of sedimentary sulfate is considered untenable. The other three models are considered to be viable, but none of them can explain all observations. The results of this study and other recent investigations prompt a re-evaluation of the sulfur budget for the 1982 El Chichón eruption. We estimate that 2.2 × 1013 g of S was emitted, and that 58 wt.% of the sulfur was present as anhydrite prior to eruption, with the remainder in a vapor phase, with H2S/SO2 ≈ 9. The bulk magmatic δ34S value for the 1982 El Chichón trachyandesite is estimated as +4.1 to +5.8‰, typical of the relatively heavy sulfur isotopic compositions that characterize subduction-related magmas.  相似文献   

18.
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   

19.
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   

20.
Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ13C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ13CDIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ13CDIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ13CDIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ13CDIC = −2.49[DIC] + 0.64, r2 = 0.84). A shallow pool fed by multiple drips shows a bimodal δ13CDIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO2 fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ13CDIC variability. Measured values of high [DIC] and low δ13CDIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ13CDIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO2 and precipitated CaCO3(1000lnα[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of 14C mass balance and paired 14C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from 14C-dead dolomite cap while the remainder of ∼77% is derived from 14C-live biomass. δ13C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ13C values calculated using the shallow pool summer/early fall data thus confirming the δ13C seasonality in both drips and coeval aragonite. δ13C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ13C records of stalagmites at DeSoto Caverns with resolving power >10−1 year will likely carry the imprints of drip annual means that record climate-driven δ13C seasonal biases.  相似文献   

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