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1.
The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl2 reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ34S values. Results show that the kerogen samples from the Cambrian have δ34S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ34S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ34S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ34S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ34S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ34S values. The relatively high δ34S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C35 homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C28 20R sterane, C23 tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C24 tetracyclic terpane, C29 hopane. Thus, δ34S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.  相似文献   

2.
Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ56Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)aq in porewaters, which generally have the lowest δ56Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ56Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ56Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ56Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ56Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.  相似文献   

3.
In this study potential iron isotope fractionation by magmatic processes in the Earth's crust was systematically investigated. High precision iron isotope analyses by MC-ICP-MS were performed on a suite of rock samples representative for the volcanic evolution of the Hekla volcano, Iceland. The whole series of Hekla's rocks results from several processes. (i) Basaltic magmas rise and induce partial melting of meta-basalts in the lower part of the Icelandic crust. The resulting dacitic magma evolves to rhyolitic composition through crystal fractionation. During this differentiation the δ56/54FeIRMM-014 values increase successively from 0.051 ± 0.021‰ for the primitive dacites to 0.168 ± 0.021‰ for the rhyolites. This increase can be described by a Rayleigh fractionation model using a constant bulk fractionation factor between all mineral phases (M) and the silicate liquid (L) of Δ56/54FeM–L = ? 0.1‰. (ii) The basaltic magma itself differentiates by crystal fractionation to basaltic andesite composition. No Fe isotope fractionation was found in this series. All basalts and basaltic andesites have an average δ56/54FeIRMM-014 value of 0.062 ± 0.042‰ (2SD, n = 9), identical to mean terrestrial basaltic values reported in previous studies. This observation is consistent with the limited removal of iron from the remaining silicate melt through crystal fractionation and small mineral-melt Fe isotope fractionation factors expected at temperatures in excess of 1050 °C. (iii) Andesites are produced by mixing of basaltic andesite with dacitic melts. The iron isotope composition of the andesites is matching that of the basaltic andesites and the less evolved dacites, in agreement with a mixing process. In the Hekla volcanic suite Li concentrations are positively correlated with indicators of magma differentiation. All Hekla rocks have δ7Li values typical for the upper mantle and demonstrate the absence of resolvable Li isotope fractionation during crystal fractionation. As a fluid-mobile trace element, Li concentrations and isotopes are a potential tracer of magma/fluid interaction. At Hekla, Li concentrations and isotope compositions do not indicate any extensive fluid exsolution. Hence, the heavy Fe isotope composition of the dacites and rhyolites can be predominately attributed to fractional crystallisation. Iron isotope analyses on single samples from other Icelandic volcanoes (Torfajökull, Vestmannaeyjar) confirm heavy Fe isotope enrichment in evolving magmas. Our results suggest that the iron isotope composition of highly evolved crust can be slightly modified by magmatic processes.  相似文献   

4.
Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redox-stratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ56Fe values between 0.3 and −1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ56Fe values down to −5‰. These low δ56Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Fe-oxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe values between −2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ56Fe values relative to river values.  相似文献   

5.
In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ56Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ56Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.  相似文献   

6.
Microbial dissimilatory iron reduction (DIR) has been identified as a mechanism for production of aqueous Fe(II) that has low 56Fe/54Fe ratios in modern and ancient suboxic environments that contain ferric oxides or hydroxides. These studies suggest that DIR could have played an important role in producing distinct Fe isotope compositions in Precambrian banded iron formations or other marine sedimentary rocks. However, the applicability of experimental studies of Fe isotope fractionation produced by DIR in geochemically simple systems to ancient marine environments remains unclear. Here we report Fe isotope fractionations produced during dissimilatory microbial reduction of hematite by Geobacter sulfurreducens in the presence and absence of dissolved Si at neutral and alkaline pH. Hematite reduction was significantly decreased by Si at alkaline (but not neutral) pH, presumably due to Si polymerization at the hematite surface. The presence of Si altered Fe isotope fractionation factors between aqueous Fe(II) or sorbed Fe(II) and reactive Fe(III), reflecting changes in bonding environment of the reactive Fe(III) component at the oxide surface. Despite these changes in isotopic fractionations, our results demonstrate that microbial Fe(III) oxide reduction produces Fe(II) with negative δ56Fe values under conditions of variable pH and dissolved Si, similar to the large inventory of negative δ56Fe in Neoarchean and Paleoproterozoic age marine sedimentary rocks.  相似文献   

7.
Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)aq - oxide interaction will produce low δ56Fe values for Fe(II)aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ56Fe Fe(II)aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ56Fe aqueous Fe(II) in many natural systems.  相似文献   

8.
The voluminous 2.5 Ga banded iron formations (BIFs) from the Hamersley Basin (Australia) and Transvaal Craton (South Africa) record an extensive period of Fe redox cycling. The major Fe-bearing minerals in the Hamersley-Transvaal BIFs, magnetite and siderite, did not form in Fe isotope equilibrium, but instead reflect distinct formation pathways. The near-zero average δ56Fe values for magnetite record a strong inheritance from Fe3+ oxide/hydroxide precursors that formed in the upper water column through complete or near-complete oxidation. Transformation of the Fe3+ oxide/hydroxide precursors to magnetite occurred through several diagenetic processes that produced a range of δ56Fe values: (1) addition of marine hydrothermal , (2) complete reduction by bacterial dissimilatory iron reduction (DIR), and (3) interaction with excess that had low δ56Fe values and was produced by DIR. Most siderite has slightly negative δ56Fe values of ∼ −0.5‰ that indicate equilibrium with Late Archean seawater, although some very negative δ56Fe values may record DIR. Support for an important role of DIR in siderite formation in BIFs comes from previously published C isotope data on siderite, which may be explained as a mixture of C from bacterial and seawater sources.Several factors likely contributed to the important role that DIR played in BIF formation, including high rates of ferric oxide/hydroxide formation in the upper water column, delivery of organic carbon produced by photosynthesis, and low clastic input. We infer that DIR-driven Fe redox cycling was much more important at this time than in modern marine systems. The low pyrite contents of magnetite- and siderite-facies BIFs suggests that bacterial sulfate reduction was minor, at least in the environments of BIF formation, and the absence of sulfide was important in preserving magnetite and siderite in the BIFs, minerals that are poorly preserved in the modern marine record. The paucity of negative δ56Fe values in older (Early Archean) and younger (Early Proterozoic) BIFs suggests that the extensive 2.5 Ga Hamersley-Transvaal BIFs may record a period of maximum expansion of DIR in Earth’s history.  相似文献   

9.
《Gondwana Research》2014,25(3):1070-1089
The Ediacaran–Cambrian was one of the most important periods for the evolution of life. Recent studies have provided detailed chemostratigraphies that decipher the linkages between ambient surface environmental changes and biological evolution. The occurrence of skeletal fossils in Ediacaran rocks suggests that the possible onset of Ca-biomineralization started in the latest Neoproterozoic. Molecular clocks also predict the emergence of animals containing Ca-carbonate spicules in the Neoproterozoic. Therefore, it is important to estimate the transition of the Ca cycle in seawater. Ancient Ca cycles in the oceans are estimated from the calcium isotopic compositions of carbonate rocks. However, the lack of continuous Ca isotopic data in the Ediacaran leaves the Ca cycle unresolved.The almost continuously exposed, Ediacaran and Cambrian strata in South China mainly comprise carbonate rocks with subordinate black shales and sandstones, which contain many fossils, suitable for the study of environmental and biological changes. We conducted drilling from the Liantuo, via the Nantuo, Doushantuo, Dengying and Yanjiahe to the Shuijingtuo formation at four sites in the Three Gorges area in order to obtain continuous, fresh samples without surface alteration and oxidation. We analyzed 44Ca/42Ca ratios in carbonate rocks with a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) screened for diagenetic alteration.The resultant δ44/42Ca ratios exhibit a smooth curve. The values of δ44/42Ca are anomalously high relative to those in the Phanerozoic, and they gradually decrease towards the end of the Ediacaran. Our new Ca isotope chemostratigraphy suggests that a different Ca cycle had existed during the Ediacaran. The long-term, high δ44/42Ca is not simply explicable by changes in temperature, differences in carbonate mineralogy, or changes in the input/output fluxes of Ca to the ocean. We propose three possible explanations for the observed high δ44/42Ca ratios in the Ediacaran: high δ44/42Ca ratios of Ca inputs, potential undiscovered sinks of Ca with low δ44/42Ca values, and negligible isotope fractionation between carbonate and seawater; we consider that one or all of these contributed to the high δ44/42Ca ratios. Of these, we prefer the small isotope fractionation, which implies that the Ca concentration in seawater was initially low in the early Ediacaran and increased throughout that period.  相似文献   

10.
We have developed a method for iron isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) using a 58Fe-54Fe double spike. A 20 min analysis produces mass-bias-corrected iron isotope data with an external reproducibility of ±0.05 (2 SD) on δ56Fe, which represents a decrease in analysis time compared to sample-standard bracketing techniques. The estimation of external reproducibility is based on replicate analysis of the ETH hematite in-house standard. The double spike method has two advantages. First, matrix effects during MC-ICP-MS analysis are decreased with tests showing that accurate iron isotope data can, in some cases, be obtained even when matrix levels exceed iron concentration (Na/Fe, Mg/Fe, and Ca/Fe up to 5, 2, and 0.1, respectively). Because chemical separation reduces matrix/Fe to levels more than three orders of magnitude lower than this, measured Fe isotope compositions are unlikely to be compromised by matrix effects. Second, it is possible to spike samples before chemical purification, which enables any isotopic fractionation effect because of incomplete recovery of iron from a sample to be accounted for. This may be important where obtaining quantitative iron yields from samples is difficult, such as the extraction of dissolved iron from water samples. Fe isotope data on a set of standard reference materials (igneous rocks, ferromanganese nodules, sedimentary rocks, and ores) are presented, which are in agreement with previously published data considering analytical uncertainties. Mantle-derived standard rock samples that are the source of iron for surficial, (bio)geochemical cycling yield a mean δ56Fe of 0.041 ± 0.11‰ (n = 8; 2 SD) with reference to IRMM-14. Hydrothermal and metamorphic calcium carbonate rocks with a relatively low iron content (100-4000 ppm) have δ56Fe = −1.25 to −0.07‰. Structural Fe(II) in hydrothermal calcites has δ56Fe = −1.25 to −0.27‰. The light iron in this range of carbonate minerals may reflect the iron isotope composition of the hydrothermal fluids from which the carbonate precipitated, or the presence of Fe(III) and/or organic material in the hydrothermal fluids during calcite precipitation.  相似文献   

11.
We propose a detailed δ13C curve for the Vendian and Lower Cambrian (Tommotian) strata of the central Siberian Platform. Two positive carbon isotope excursions identified near the base of the Yuryakh Formation (up to 5.5‰) and in the lower Bilir Formation (up to 5‰) are assigned to the lowermost and middle Tommotian, respectively. This correlation is supported by paleontological data, specific 87Sr/86Sr values (0.70845-0.70856), and similar C isotope record in coeval Early Cambrian basins. The documented minor vertical oscillations (a few meters) of these isotope excursions relative to the formation boundaries in remote boreholes is presumably caused by the spatiotemporal migration of facies. A high-amplitude negative δ13C excursion (-8 to -11‰) in the upper Nepa Regional Stage putatively corresponds to the global Shuram-Wonoka negative carbon isotope excursion (Middle Ediacaran). Carbonates of the lower Nepa Regional Stage (Besyuryakh Formation) demonstrate positive δ13C values (up to 5‰) and minimum 87Sr/86Sr ratios of 0.70796-0.70832. The C and Sr isotope record of the Nepa Regional Stage provides its robust correlation with the Dal’nyaya Taiga and Zhuya Groups of the Patom Foredeep. Micropaleontological data herein reported and glacial diamictites documented at the base of the Vendian sedimentary cover both in the central Patom Foredeep and on its periphery suggest a full stratigraphic volume of the Ediacaran System in the most stratigraphically complete sections of the central Siberian Platform.  相似文献   

12.
Iron isotope compositions of suspended particulate matters (SPM) collected from the Aha Lake, an artificial lake in the karst area of Yun-Gui Plateau, and its tributaries in summer and winter were investigated for our understanding of the behavior of Fe isotopes during iron biogeochemical cycling in lake. δ56Fe values of SPM display statistically negative shift relative to IRMM-014. Samples from the lake display a range from ?1.36‰ to ?0.10‰ in summer and from ?0.30‰ to ?0.07‰ in winter, while river samples vary from ?0.88‰ to 0.07‰ in summer and from ?0.35‰ to ?0.03‰ in winter. The average iron isotope composition of aerosol samples is + 0.10‰, which is very similar to that of igneous rocks (0.09‰). The SPM in most rivers and water column showed seasonal variation in δ56Fe value: the δ56Fe values of SPM in summer were lower than in winter. The seasonal variation in δ56Fe value of the riverine SPM should be ascribed to the change in source of particulate Fe and geochemical process in the watershed: More particulate Fe was leached from soil and produced by weathering of pyrite widely distributed in coal-containing strata. It is suggested that both allochthonous inputs and the redox iron cycling control the variations of δ56Fe values for SPM in lake.During summer stratification, an Fe cycle named “ferrous wheel” is established near the redox boundary where the upwardly diffusing Fe(II) is oxidized and the reactive Fe oxides formed will continuously sink back into the reduction zone to complete the cycle. The δ56Fe values for SPM reach the minima, ?0.88‰ for DB station and ?1.36‰ for LJK station, just near the redox boundary as a result of the Fe cycling, where a rough 45% to 76% of Fe in these particles was produced by the repetitive cycle. Due to random transportation and diffusion, δ56Fe values of the particles near the redox zone distributed into approximately a Gaussian shape. The good negative correlation existed between δ56Fe values and Fe/Al ratios for DB station, suggesting that they together can be used as good indicators of the redox-driven Fe transformations.  相似文献   

13.
This work presents isotopic data for the non-traditional isotope systems Fe, Cu, and Zn on a set of Chicxulub impactites and target lithologies with the aim of better documenting the dynamic processes taking place during hypervelocity impact events, as well as those affecting impact structures during the post-impact phase. The focus lies on material from the recent IODP-ICDP Expedition 364 Hole M0077A drill core obtained from the offshore Chicxulub peak ring. Two ejecta blanket samples from the UNAM 5 and 7 cores were used to compare the crater lithologies with those outside of the impact structure. The datasets of bulk Fe, Cu, and Zn isotope ratios are coupled with petrographic observations and bulk major and trace element compositions to disentangle equilibrium isotope fractionation effects from kinetic processes. The observed Fe and Cu isotopic signatures, with δ56/54Fe ranging from ?0.95‰ to 0.58‰ and δ65/63Cu from ?0.73‰ to 0.14‰, mostly reflect felsic, mafic, and carbonate target lithology mixing and secondary sulfide mineral formation, the latter associated to the extensive and long-lived (>105 years) hydrothermal system within Chicxulub structure. On the other hand, the stable Zn isotope ratios provide evidence for volatility-governed isotopic fractionation. The heavier Zn isotopic compositions observed for the uppermost part of the impactite sequence and a metamorphic clast (δ66/64Zn of up to 0.80‰ and 0.87‰, respectively) relative to most basement lithologies and impact melt rock units indicate partial vaporization of Zn, comparable to what has been observed for Cretaceous-Paleogene boundary layer sediments around the world, as well as for tektites from various strewn fields. In contrast to previous work, our data indicate that an isotopically light Zn reservoir (δ66/64Zn down to ?0.49‰), of which the existence has previously been suggested based on mass balance considerations, may reside within the upper impact melt rock (UIM) unit. This observation is restricted to a few UIM samples only and cannot be extended to other target or impact melt rock units. Light isotopic signatures of moderately volatile elements in tektites and microtektites have previously been linked to (back-)condensation under distinct kinetic regimes. Although some of the signatures observed may have been partially overprinted during post-impact processes, our bulk data confirm impact volatilization and condensation of Zn, which may be even more pronounced at the microscale, with variable degrees of mixing between isotopically distinct reservoirs, not only at proximal to distal ejecta sites, but also within the lithologies associated with the Chicxulub impact crater.  相似文献   

14.
Geochemical and iron isotopic compositions of magnetite, ilmenite and pyrite separates from the FeTi oxide ores hosted in the Damiao anorthosite-type FeTi ore deposit were analyzed to investigate sub-solidus cooling history of the titanomagnetite. The FeTi oxides form two series of solid solutions, namely, ulvöspinel-magnetite (Usp-Mtss) and hematite-ilmenite (Hem-Ilmss) solid solutions. The magnetite separates have 14–27 mol% ulvöspinel, while the ilmenite separates have 5–8 mol% hematite. Major element compositions of the mineral separates suggest that the ilmenites were mainly exsolved from the Usp-Mtss by oxidation of ulvöspinel in the temperature range of ~820–600 °C and experienced inter-oxide re-equilibration with the magnetites. Associated with the exsolution is the substantial inter-mineral iron isotope fractionation. The magnetite separates are characterized by high δ57Fe (+0.27 − +0.65‰), whereas the ilmenite separates have lower δ57Fe (−0.65 to −0.28‰). Two types of pyrite are petrographically observed, each of which has a distinctive iron isotope fingerprint. Type I pyrite (pyriteI) with higher δ57Fe (δ57Fe = +0.63 − +0.95‰) is consistent with magmatic origin, and type II pyrite (pyriteII) with lower δ57Fe (δ57Fe = −0.90 to −0.11‰) was likely to have precipitated from fluids. Iron isotopic fingerprints of the pyriteI probably indicate variations of oxygen fugacity, whereas those of the pyriteII may result from fluid activities. The iron isotopic fractionation between the magnetite and ilmenite is the net result of sub-solidus processes (including ulvöspinel oxidation and inter-oxide re-equilibration) without needing varying oxygen fugacity albeit its presence. Although varying composition of magnetite-ilmenite pairs reflects variations of oxygen fugacity, inter-oxide iron isotopic fractionation does not.  相似文献   

15.
《Chemical Geology》2006,225(1-2):61-76
The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ11B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ11B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ11B of Cretaceous seawater was close to the present-day value. Low δ11B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ11B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.  相似文献   

16.
The discovery of the Gouap banded iron formations(BIFs)-hosted iron mineralization in the northwestern of the Nyong Group(Ntem Complex)in southwestern Cameroon provides unique insights into the geology of this region.In this contribution,we firstly report detailed study of geochemistry,isotopic and geochronology of well preserved samples of the Gouap BIFs collected from diamond drillcores.The Gouap BIFs consist mainly of amphibole BIFs and amphibole-pyrite BIFs characterized by dominant Fe2O3+SiO2contents and variable contents of CaO,MgO and SO3,consistent with the presence of amphibole,chlorite,epidote and pyrite,formed during amphibolite facies metamorphism and overprinted hydrothermal event.The amphibole–pyrite BIFs are typically enriched in trace and rare earth elements(REE)compared to the amphibole BIFs,suggesting the influence of detrital materials as well as secondary hydrothermal alteration.The Post Archean Australian Shale(PAAS)-normalized REE–Y profiles of the Gouap BIFs display positive La,Eu anomalies,weak negative Ce anomalies,indicating a mixture of low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.We present here the first isotopic data of BIFs within the Ntem Complex.Theδ30SiNBS28values of the quartz from the Gouap BIFs vary from-1.5‰to-0.3‰and from-0.8‰to-0.9‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.The quartz hasδ18OV-SMOW values of 6.8‰–9.5‰(amphibole BIFs)and 9.2‰–10.6‰(amphibole–pyrite BIFs).The magnetite from the Gouap BIFs showsδ18O values ranging from-3.5‰to-1.8‰and from-3‰to-1.7‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.Moreover,the pyrite grains in the amphibole–pyrite BIFs displayδ34S values of 1.1‰–1.8‰.All isotopic data of the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital input distant from the volcanic activity.According to their geochemical and isotopic characteristics,we propose that the Gouap BIFs belong to the Superior type.In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of zircon in thin section.The Gouap BIFs were probably deposited at 2422±50 Ma in a region where sediments extended from continental shelf to deep-water environments along craton margins like the Caue Formation of the Minas Supergroup,Brazil.The studied BIFs have experienced regional hydrothermal activity and metamorphism at 2089±8.3 Ma during the Eburnean–Transamazonian orogeny.These findings suggest a physical continuity between the protocratonic masses of both Sao Francisco and Congo continents in the Rhyacian Period.  相似文献   

17.
The iron stable isotope compositions (δ56Fe) and iron valence states of ultrahigh‐pressure eclogites from Bixiling in the Dabie orogen belt, China, were measured to trace the changes of geochemical conditions during vertical transportation of earth materials, for example, oxygen fugacity. The bulk Fe3+/ΣFe ratios of retrograde eclogites, determined by Mössbauer spectroscopy, are consistently higher than those of fresh eclogites, suggesting oxidation during retrograde metamorphism and fluid infiltration. The studied eclogites (five samples) display limited mid‐ocean ridge basalts (MORB)‐like (~0.10‰) δ56Fe values, which are indistinguishable from their protoliths, that is, gabbro cumulates formed through differentiation of mantle‐derived basaltic magma. This suggests that Fe isotope fractionation during continental subduction is limited. Garnet separates display limited δ56Fe variation ranging from ?0.08 ± 0.07 ‰ to 0.02 ± 0.07‰, whereas coexisting omphacite displays a large variation of δ56Fe values from 0.15 ± 0.07‰ to 0.47 ± 0.07‰. Omphacite also has highly variable Fe3+/ΣFe ratios from 0.367 ± 0.025 to 0.598 ± 0.024, indicating modification after peak metamorphism. Omphacite from retrograde eclogites has elevated Fe3+/ΣFe ratios (0.54–0.60) compared to that from fresh eclogites (~0.37), whereas garnet displays a narrow range of ferric iron content with Fe3+/ΣFe ratios from 0.039 ± 0.013 to 0.065 ± 0.022. The homogenous δ56Fe values and Fe3+/ΣFe ratios of garnet suggest that it survived the retrograde metamorphism and preserved its Fe‐isotopic features and ferric contents of peak metamorphism. Because of similar diffusion rates of Fe and Mg in garnet and omphacite, and constant Δ26Mgomphacite‐garnet values (1.14 ± 0.04‰), equilibrium iron isotope fractionation between garnet and omphacite was probably achieved during peak metamorphism. Elevated Fe3+/ΣFe ratios of omphacite from retrograde eclogites and variant Δ56Feomphacite‐garnet values of the studied eclogites (0.13 ± 0.10‰ to 0.48 ± 0.10‰) indicate that oxidized geofluid infiltration resulted in the elevation of δ56Fe values of omphacite during retrograde metamorphism.  相似文献   

18.
This study investigated the geochemical features of the lower Paleozoic strata of Yaerdang Mountain outcrop along with the core samples from well TD2∈ in the eastern Tarim Basin,NW China.The total organic carbon abundance,hydrocarbon-generating precursor biospecies,and stable isotope ratios of organics and carbonate(δ~(13)C_(ker),δ~(13)C_(carb) and δ~(18)O_(carb)) were comprehensively studied for their possible correlative constraints during sedimentary evolution.The results revealed that the δ~(13)C_(ker)(VPDB) of Cambrian kerogens along the outcrop section varied from-34.6‰ to-28.4‰,indicating an increasing tendency from the lower Cambrian to the upper Cambrian.This was on the whole accompanied by the variation in the δ~(13)C_(carb) and δ~(18)O_(carb) along the profile,which might be associated with the changes in the sea level and also in the compositional variation of benthic and planktonic biomass.The large variation in the stable carbon isotope ratios up to 6‰ along the outcrop section reflected the heterogeneity of the Cambrian source rocks from the eastern Tarim Basin.Hence,the ~(13)C-enriched crude oils from well TD2∈might have been derived from a localized stratum of Cambrian source rocks.The results from this study showed the possibility of multiple source kitchens in the Cambrian-lower Ordovician portion of Tarim Basin.  相似文献   

19.
The Han-Xing iron mineralization in the central North China Craton is a typical Fe skarn deposit associated with altered diorites. Here we report the Fe isotopic compositions of whole rocks and mineral separates from this deposit with a view to evaluate the Fe isotope fractionation during the formation of Fe skarn deposit, and to constrain the metal source. The Fe isotopes show a large variation both in whole rocks and mineral separates. Altered diorites show a wide range in δ56Fe values (− 0.07‰ to + 0.21‰ relative to the Fe isotope standard IRMM-014) which positively correlate with their TFe2O3/TiO2 ratios (Fe2O3 and FeO calculated as TFe2O3). The positive correlation indicates that heavy Fe isotopes were preferentially leached from diorites during the skarn-type alteration. Among the metallic minerals, pyrite and pyrrhotite are isotopically heavier (+ 0.12‰ to + 0.48‰) than the magnetite (+ 0.07‰ to + 0.21‰). Fe isotope fractionation between mineral pairs demonstrates that magnetite did not attain Fe isotopic equilibrium with pyrite and pyrrhotite, whereas pyrite and pyrrhotite might have attained isotopic equilibrium. Petrological observations and major element data also suggest that iron was leached from the diorites during the skarn-type alteration. If the leached iron provides the main Fe budget of the Han-Xing Fe skarn deposit, magnetite in ores would be isotopically heavier than the unaltered diorite. However, our results are in contrast with the magnetite being isotopically lighter than the unaltered diorite. This suggests that the major Fe source of the Han-Xing Fe skarn deposit is not from the leaching of diorites, and might be from magmatic fluid which is isotopically lighter than the silicate melt. Our data demonstrate that Fe isotopes can be used as important tracers in deciphering the metal source of Fe skarn deposits.  相似文献   

20.
《Gondwana Research》2014,25(3):1090-1107
The Ediacaran and Cambrian periods were one of the most important periods for the evolution of life. The biodiversity drastically expanded in the period. However, the origins are still ambiguous because surface environmental changes through the time have not been well understood yet. We conducted in-situ analyses of the phosphorus contents of carbonate minerals with a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) to estimate the phosphorus contents of seawater from the Ediacaran to the early Cambrian. Carbonate rocks contain not only the carbonate minerals but also detrital and authigenic materials such as silicate and phosphate minerals. Therefore, the whole rock compositions of carbonate rocks are not directly related with seawater composition. To avoid the influence of the involvement of the phosphate minerals, we performed the microscopic observation, elemental mapping of Si, Ca, Mg, Fe, and P contents with an electron probe microanalyzer (EPMA), and investigation of time profiles of signal intensities of Ca, Sr, Mn, P, La and Ba with the LA-ICP-MS. Especially, samples with low Mn/Sr ratios and primary textures such as oolites are suitable to estimate the primary phosphorus contents of the carbonates.The chemostratigraphy of the phosphorus contents of carbonates from the drill core and outcrop samples displays that the phosphorus contents decrease from ca. 400 ppm in the Ediacaran through ca. 200 ppm around the terminal Ediacaran and the beginning of the Cambrian to ca. 50 ppm in the early Cambrian. Previous works on 87Sr/86Sr chemostratigraphy from the Ediacaran to the Cambrian sections suggested relatively high continental influx in the middle Ediacaran, and around the Precambrian–Cambrian (PC/C) boundary. The high phosphorus content in the Ediacaran was possibly due to the high continental flux. On the other hand, previous works on chemostratigraphy of carbon isotope values of carbonate carbon from the Ediacaran to the Cambrian sections showed some large negative anomalies in the Ediacaran and around the Precambrian–Cambrian (PC/C) boundary, and suggested that the negative anomalies were caused by remineralization and respiration of dissolved organic matter. The degradation of the organic matter also accounts for the high phosphorus contents in the Ediacaran. The high phosphorus content of seawater favors enhancement of primary productivity and formation of phosphorites. The high phosphorus contents in the seawater possibly led to the emergence of the large, and motile organism through the enhancement of primary productivity and the consequent increase of oxygen content of the seawater.  相似文献   

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