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1.
Abstract Positive shifts in global seawater δ13CDIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ18O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ13C and δ18O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and 13C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate 13C and 18O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.  相似文献   

2.
Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ13C and δ18O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ13C and δ18O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ13C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ13C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.  相似文献   

3.
Twenty-three magnesite samples from vein deposits, found in ultramafic rocks related to ophiolites in the north-east Bohemian Massif, have been examined for carbon and oxygen isotope ratios. In these rocks two stages of antigorite serpentinization took place prior to magnesite precipitation. δ18OSMOW in magnesites ranges from 24.5 to 27.9%o (corrected for acid fractionation factor) which leads us to conclude a meteoric origin of the ore-forming solution. This inference is further supported by δ13C values (?18.7 to ?4.4%o) which point to a biogenic origin of carbon in the magnesites.  相似文献   

4.
The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ13CVPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ18OVPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ18O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of 18O‐depleted water lowered the δ18O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.  相似文献   

5.
Oxygen isotopic compositions of silicates in eclogites and whiteschists from the Kokchetav massif were analyzed by whole‐grain CO2‐laser fluorination methods. Systematic analyses yield extremely low δ18O for eclogites, as low as ?3.9‰ for garnet; these values are comparable with those reported for the Dabie‐Sulu UHP eclogites. Oxygen isotopic compositions are heterogeneous in samples of eclogite, even on an outcrop scale. Schists have rather uniform oxygen isotope values compared to eclogites, and low δ18O is not observed. Isotope thermometry indicates that both eclogites and schists achieved high‐temperature isotopic equilibration at 500–800 °C. This implies that retrograde metamorphic recrystallization barely modified the peak‐metamorphic oxygen isotopic signatures. A possible geological environment to account for the low‐δ18O basaltic protolith is a continental rift, most likely subjected to the conditions of a cold climate. After the basalt interacted with low δ18O meteoric water, it was tectonically inserted into the surrounding sedimentary units prior to, or during subduction and UHP metamorphism.  相似文献   

6.
Carbonate mud that accumulated in the deep parts of a late Kimmeridgian carbonate ramp (Iberian Basin, NE Spain) was partly derived by resedimentation from shallow water production areas. High-frequency sea-level changes, probably driven by climatic changes in tune with precession and short-eccentricity cycles, affected carbonate production and the amount of exported sediment. Facies analysis and correlation of three outcrops located in middle and outer ramp settings allows a comparison of high-order sequences (bundles of beds and sets of bundles) across a ramp transect and an assessment of the carbonate factory. Analysis of the storm deposits found in middle ramp settings identifies deepening to shallowing high-frequency cycles based on the level of exported carbonate. In outer ramp areas, many of the bundles exhibit a thinning trend, indicating a progressive decrease of carbonate production and hence, carbonate export during periods of high-frequency sea-level rise. δ13Ccarb values show a gradual increase through the studied long-term transgressive interval ranging from 1·5‰ to 2·8‰. Within this long-term evolutionary trend, short-term δ13Ccarb fluctuations occur that correspond with some of the high-order cycles defined from sedimentary facies analysis. These short-term δ13Ccarb shifts are interpreted as shifts in carbonate export from shallow reef regions to the outer ramp. A consequence of this study is that variation in δ13Ccarb can be used for correlation in outer ramp successions, at least on a basin-wide scale.  相似文献   

7.
The Late Neoproterozoic Buah Formation (Nafun Group, Oman) is a carbonate unit outcropping in the Jabal Akhdar and Huqf areas. It is composed mostly of shallow‐water carbonates deposited on a distally steepened carbonate ramp. Correlation of two δ13C isotope shifts shows that in the Jabal Akhdar ramp differentiation into fast and slow subsiding areas was followed by lateral progradation. In the Huqf area, however, a uniform scenario of upward shallowing of the facies and lateral progradation is demonstrated by chemostratigraphic timelines cross‐cutting the facies belts. The chemostratigraphic profiles show that the Buah Formation was deposited during sea‐level highstand conditions and that ramp differentiation was due to synsedimentary tectonics. High‐resolution correlation of δ13C profiles from the same lithostratigraphic unit (whether Precambrian or Phanerozoic in age) lacking biostratigraphic data can shed light on carbonate systems dynamics, tectonic vs. eustatic controls on depositional sequences and basin subsidence.  相似文献   

8.
We report δ44/40Ca(SRM 915a) values for eight fused MPI‐DING glasses and the respective original powders, six USGS igneous rock reference materials, the U‐Th disequilibria reference material TML, IAEA‐CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM‐GEOMAR and Saskatchewan Isotope Laboratory) using 43Ca/48Ca‐ and 42Ca/43Ca‐double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2‰ at the 95% confidence level. The impact of different preparation methods on the δ44/40Ca(SRM 915a) values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ44/40Ca(SRM 915a) values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of δ44/40Ca(SRM 915a) values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS‐1 (1.49 ± 0.06‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in 44Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in 44Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.  相似文献   

9.
Boron isotope data are presented for Cenozoic Western Anatolia rocks, which define two main associations: (i) calc-alkaline, shoshonitic and ultra-potassic rocks (Early to Middle Miocene); and (ii) Late Miocene–Quaternary intraplate alkali basalts. Boron data, together with Sr–Nd isotope and other trace elements, are consistent with a progressive dehydration of the slab, producing fluid phases gradually depleted in B (and 11B). These fluids were added to the supraslab mantle, triggering a partial melting that gave rise to orogenic magmatism. The stretching and tearing of the slab caused by the faster convergence of Greece over Africa with respect to Anatolia facilitated an interaction of the upwelling subslab asthenosphere with residual slab-fluids during the Late Miocene followed by production of typical intraplate magmas during the Pleistocene–Holocene, whose relatively high δ11B (approximately −2‰) is considered representative of the local asthenosphere not affected by subduction contamination.  相似文献   

10.
《Geochimica et cosmochimica acta》1999,63(13-14):2001-2007
Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ18O of the foraminiferal calcite decreases with increasing CO32− concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H2CO3] + [HCO3−] + [CO32−] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO3 also decreases with increasing pH. The slope of shell δ18O vs. [CO32−] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg−1)−1 (Spero et al., 1997), whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg−1)−. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed.  相似文献   

11.
The effects of phosphate speciation on both rates of isotopic exchange and oxygen isotope equilibrium fractionation factors between aqueous phosphate and water were examined over the temperature range 70 to 180°C. Exchange between phosphate and water is much faster at low pH than at high pH, an observation that is similar to what has been observed in the analogous sulfate-water system. Oxygen isotope fractionations between protonated species like H3PO4 and H2PO4− that are dominant at relatively low pH and species like PO43− and ion pairs like KHPO4− that are dominant at relatively high pH, range between 5 and 8‰ at the temperatures of the experiments. In aqueous phosphate systems at equilibrium, 18O/16O ratios increase with increasing degree of protonation of phosphate. This effect can be explained in part by the relative magnitudes of the dissociation constants of the protonated species. Under equilibrium conditions, carbonate in solution or in solid phases concentrates 18O relative to orthophosphate in solution or in solid phases at all temperatures, supporting the traditional view that biogenic phosphate is precipitated in near oxygen isotope equilibrium with body/ambient aqueous fluids with no attendant vital effects.  相似文献   

12.
Dark grey, bituminous dolostones interbedded with marine-derived anhydrite horizons occur in the Triassic Reichenhall Formation of western Austria. Fossils are rare and indicate a hostile, hypersaline depositional environment. The dolomites are finely crystalline, fairly stoichiometric, well ordered and non-ferroan. Closely spaced samples (94 in total) of individual dolomite units have been analysed for their carbon and oxygen isotopic composition. The data indicate surprisingly low δ18O values (-5.7 to -2.1%0 PDB), whereas the δ13C values are comparable to the contemporary Triassic seawater (+0.2 to +2.6%0 PDB). Sedimentological evidence, including (i) lack of any evidence for extensive dissolution, (ii) distinct oxygen and carbon isotope ratios of individual dolomite units, (iii) covariance of carbon and oxygen isotopes within some dolomite layers and (iv) inclusions of celestite in dolomite, indicates a nearly closed system after early diagenesis. Combining this information with water-rock interaction calculations suggests that the lightest oxygen isotope compositions are the result of freshwater influx into the basin during very early dolomite formation. A secondary factor may be dolomite recrystallization at elevated temperatures during burial.  相似文献   

13.
This paper addresses global oxygenation and establishment of a marine sulphate reservoir in the Palaeoproterozoic. We report syn-depositional, marine, anhydrite-containing pseudomorphs after Ca-sulphates as widespread throughout the Tulomozero Formation in the SE Fennoscandian Shield, implying that surface waters were oxidized and a large SO marine reservoir was developed as early as 2100 Ma. The Ca-sulphates and associated magnesite and halite precipitated syn-depositionally from oxidized, evolved and modified seawater in coastal playa, sabkha and intertidal flat settings. 87Sr/86Sr and δ13C of associated 13C-rich stromatolitic dolostones were environmentally controlled with the highest ratios occurring in playa and sabkha carbonates. The results imply that the Palaeoproterozoic δ13Ccarb excursion was amplified by 8‰ by local environmental factors and calls into question many observations of putative δ13C global signals reported previously from similar Palaeoproterozoic, evaporitic, dolostones. The local environmental amplification can explain a large regional and intercontinental δ13C discrepancy observed in synchronous carbonates.  相似文献   

14.
Laboratory experiments on reagent-grade calcium carbonate and carbonate rich glacial sediments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis and early stages of carbonate dissolution driven by atmospheric CO2. There is preferential dissolution of Ca12CO3 during hydrolysis, resulting in δ13C-DIC values that are significantly lighter isotopically than the bulk carbonate. The fractionation factor for this kinetic isotopic effect is defined as εcarb. εcarb is greater on average for glacial sediments (−17.4‰) than for calcium carbonate (−7.8‰) for the < 63 μm size fraction, a sediment concentration of 5 g L−1 and closed system conditions at 5°C. This difference is most likely due to the preferential dissolution of highly reactive ultra-fine particles with damaged surfaces that are common in subglacial sediments. The kinetic isotopic fractionation has a greater impact on δ13C-DIC at higher CaCO3:water ratios and is significant during at least the first 6 h of carbonate dissolution driven by atmospheric CO2 at sediment concentrations of 5 g L−1. Atmospheric CO2 dissolving into solution following carbonate hydrolysis does not exhibit any significant equilibrium isotopic fractionation for at least ∼ 6 h after the start of the experiment at 5°C. This is considerably longer than previously reported in the literature. Thus, kinetic fractionation processes will likely dominate the δ13C-DIC signal in natural environments where rock:water contact times are short <6-24 h (e.g., glacial systems, headwaters in fluvial catchments) and there is an excess of carbonate in the sediments. It will be difficult apply conventional isotope mass balance techniques in these types of environment to identify microbial CO2 signatures in DIC from δ13C-DIC data.  相似文献   

15.
《Geochimica et cosmochimica acta》1999,63(11-12):1825-1836
Oxygen isotope data have been obtained for silicate inclusions in diamonds, and similar associated minerals in peridotitic and eclogitic xenoliths from the Finsch kimberlite by laser-fluorination. Oxygen isotope analyses of syngenetic inclusions weighing 20–400 μg have been obtained by laser heating in the presence of ClF3. 18O/16O ratios are determined on oxygen converted to CO2 over hot graphite and, for samples weighing less than 750 μg (producing <12 μmoles O2) enhanced CO production in the graphite reactor causes a systematic shift in both δ13C and δ18O that varies as a function of sample weight. A “pressure effect” correction procedure, based on the magnitude of δ13C (CO2) depletion relative to δ13C (graphite), is used to obtain corrected δ18O values for inclusions with an accuracy estimated to be ±0.3‰ for samples weighing 40 μg.Syngenetic inclusions in host diamonds with similar δ13C values (−8.4‰ to −2.7‰) have oxygen isotope compositions that vary significantly, with a clear distinction between inclusions of peridotitic (+4.6‰ to +5.6‰) and eclogitic paragenesis (+5.7‰ to +8.0‰). The mean δ18O composition of olivine inclusions is indistinguishable from that of typical peridotitic mantle (5.25 ± 0.22‰) whereas syngenetic purple garnet inclusions possess relatively low δ18O values (5.00 ± 0.33‰). Reversed oxygen isotope fractionation between olivine and garnet in both diamond inclusions and diamondiferous peridotite xenoliths suggests that garnet preserves subtle isotopic disequilibrium related to genesis of Cr-rich garnet and/or exchange with the diamond-forming fluid. Garnet in eclogite xenoliths in kimberlite show a range of δ18O values from +2.3‰ to +7.3‰ but garnets in diamondiferous eclogites and as inclusions in diamond all have values >4.7‰.  相似文献   

16.
Abstract Petrological, oxygen isotope and 40Ar/39Ar studies were used to constrain the Tertiary metamorphic evolution of the lower tectonic unit of the Cyclades on Tinos. Polyphase high-pressure metamorphism reached pressures in excess of 15 kbar, based on measurements of the Si content in potassic white mica. Temperatures of 450–500° C at the thermal peak of high-pressure metamorphism were estimated from critical metamorphic assemblages, the validity of which is confirmed by a quartz–magnetite oxygen isotope temperature of 470° C. Some 40Ar/39Ar spectra of white mica give plateau ages of 44–40 Ma that are considered to represent dynamic recrystallization under peak or slightly post-peak high-pressure metamorphic conditions. Early stages in the prograde high-pressure evolution may be documented by older apparent ages in the high-temperature steps of some spectra. Eclogite to epidote blueschist facies mineralogies were partially or totally replaced by retrograde greenschist facies assemblages during exhumation. Oxygen isotope thermometry of four quartz–magnetite pairs from greenschist samples gives temperatures of 440–470° C which cannot be distinguished from those deduced for the high-pressure event. The exhumation and overprint is documented by decreasing ages of 32–28 Ma in some greenschists and late-stage blueschist rocks, and ages of 30–20 Ma in the lower temperature steps of the Ar release patterns of blueschist micas. Almost flat parts of Ar–Ar release spectra of some greenschist micas gave ages of 23–21 Ma which are assumed to represent incomplete resetting caused by a renewed prograde phase of greenschist metamorphism. Oxygen isotope compositions of blueschist and greenschist facies minerals show no evidence for the infiltration of a δ18O-enriched fluid. Rather, the compositions indicate that fluid to rock ratios were very low, the isotopic compositions being primarily controlled by those of the protolith rocks. We assume that the fundamental control catalysing the transformation of blueschists into greenschists and the associated resetting of their isotopic systems was the selective infiltration of metamorphic fluid. A quartz–magnetite sample from a contact metamorphic skarn, taken near the Miocene monzogranite of Tinos, gave an oxygen isotope temperature of 555° C and calculated water composition of 9.1%. The value of δ18O obtained from this water is consistent with a primary magmatic fluid, but is lower than that of fluids associated with the greenschist overprint, which indicates that the latter event cannot be directly related to the monozogranite intrusion.  相似文献   

17.
Water temperature, oxygen isotope composition and the δ13C of dissolved inorganic carbon were measured in 2 southern Michigan rivers, the Huron River and Fleming Creek, between late September 1990 and June 1992. The final full year of shell growth in 3 unionids collected in 1992 from these rivers was sampled for stable isotope analysis with a resolution of 30 μm. The δ18O of both shell nacre and the prismatic layer is accurately predicted by a fractionation relationship developed for biogenic aragonite. High resolution sampling of 3 species and bulk sampling of 3 other species suggest that all unionids adhere to this oxygen isotope fractionation relationship. This relationship is used to show that shell growth ceases below approximately 12°C. In these 2 settings the average δ18O value of shell (PDB scale) is within 0.5‰ of the average δ18O of river water (SMOW scale). Unionids can therefore be used in oxygen-isotope-based paleoclimatic and paleohydrologic reconstructions. In contrast, the carbon isotope ratio of shell is not accurately predicted by published fractionation factors between D.I.C. and carbonate. Shell δ13C is more negative than predicted values and the offset is highly variable suggesting a significant and variable incorporation of metabolic carbon into the shell carbonate.  相似文献   

18.
Matrix micrites are a commonly used carbonate archive for the reconstruction of past environmental parameters, but one that is submitted to known limitations. Main reasons for the often ambiguous value of many micrite-based isotope data sets are the unknown origin of the micrite components and their poorly resolved diagenetic history. Here we present carbon and oxygen-isotope data retrieved from Oxfordian to Tithonian Ammonitico Rosso nodular micrites sampled from three sections in the Betic Cordillera (Southern Spain). All three sections were correlated and sampled using a rigorous biostratigraphic framework. A noteworthy feature is that analyzed matrix micrites are more conservative in terms of their isotopic composition than other carbonate materials commonly considered to resist diagenetic alteration under favourable circumstances. Remarkably, this refers not only to δ13C ratios, which reflect the typical Late Jurassic global trend, but also to δ18O ratios that range around 0.3‰. The 18O-enriched oxygen-isotope ratios are considered to represent diagenetic stabilization of carbonate ooze under the influence of marine porewaters within the sediment–water interphase (i.e., the immature sedimentary section, usually submitted to biogenic activity). This interpretation agrees with the very early lithification of micrite nodules with cements precipitated from marine porewaters, enriched by the dissolution of aragonite skeletals (i.e., ammonite shells). According to the model proposed, low sedimentation rates as well as rapid early marine differential cementation, under the influence of currents and seawater pumping, affected the sediment–water interphase of epioceanic swells where deposition resulted in early lithified Ammonitico Rosso facies. The data obtained show that special care must be taken to prevent oversimplified interpretations of carbonate archives, particularly in the context of epioceanic settings.  相似文献   

19.
Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ13C values of CO2 to trace the migration of injected CO2 in the subsurface. More recently the use of δ18O values of both CO2 and reservoir fluids has been proposed as a method for quantifying in situ CO2 reservoir saturations due to O isotope exchange between CO2 and H2O and subsequent changes in δ18OH2O values in the presence of high concentrations of CO2. To verify that O isotope exchange between CO2 and H2O reaches equilibrium within days, and that δ18OH2O values indeed change predictably due to the presence of CO2, a laboratory study was conducted during which the isotope composition of H2O, CO2, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO2 pressures. Conditions typical for the Pembina Cardium CO2 Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ18O values of CO2 were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using 18O enriched water for the experiments it was demonstrated that changes in the δ18O values of water were predictably related to the fraction of O in the system sourced from CO2 in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO2 is related to the total volumetric saturation of CO2 and water as a fraction of the total volume of the system, it is concluded that changes in δ18O values of reservoir fluids can be used to calculate reservoir saturations of CO2 in CCS settings given that the δ18O values of CO2 and water are sufficiently distinct.  相似文献   

20.
Accurate constraints on past ocean temperatures and compositions are critical for documenting climate change and resolving its causes. Most proxies for temperature are not thermodynamically based, appear to be subject to biological processes, require regional calibrations, and/or are influenced by fluid composition. As a result, their interpretation becomes uncertain when they are applied in settings not necessarily resembling those in which they were empirically calibrated. Independent proxies for past temperature could provide an important means of testing and/or expanding on existing reconstructions. Here we report measurements of abundances of stable isotopologues of calcitic and aragonitic benthic and planktic foraminifera and coccoliths, relate those abundances to independently estimated growth temperatures, and discuss the possible scope of equilibrium and kinetic isotope effects. The proportions of 13C-18O bonds in these samples exhibits a temperature dependence that is generally similar to that previously been reported for inorganic calcite and other biologically precipitated carbonate-containing minerals (apatite from fish, reptile, and mammal teeth; calcitic brachiopods and molluscs; aragonitic coral and mollusks). Most species that exhibit non-equilibrium 18O/16O (δ18O) and 13C/12C (δ13C) ratios are characterized by 13C-18O bond abundances that are similar to inorganic calcite and are generally indistinguishable from apparent equilibrium, with possible exceptions among benthic foraminiferal samples from the Arctic Ocean where temperatures are near-freezing. Observed isotope ratios in biogenic carbonates can be explained if carbonate minerals generally preserve a state of ordering that reflects the extent of isotopic equilibration of the dissolved inorganic carbon species.  相似文献   

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