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1.
Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ18O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ18O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO2 and aqueous HCO?3. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ18O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.  相似文献   

2.
Plio‐Pleistocene speleothems from australopithecine‐bearing caves of South Africa have the potential to yield paleoenvironmental and geochronological information using isotope geochemistry. Prior to such studies it is important to assess the preservation of geochemical signals within the calcitic and aragonitic speleothems, given the tendency of aragonitic speleothems to recrystallize to calcite. This study documents the geochemical suitability of speleothems from the principal hominin‐bearing deposits of South Africa. We use petrography, together with stable isotope and trace element analysis, to identify the occurrence of primary aragonite, primary calcite, and secondary calcite. This study highlights the presence of diagenetic alteration at many of the sites, often observed as interbedded primary and secondary fabrics. Trace element and stable isotopic values distinguish primary calcite from secondary calcite and offer insights into geochemical aspects of the past cave environment. δ13C values of the primary and secondary calcites range from +6 to −9‰ and δ18O values range from −4 to −6‰. The data are thus typical of meteoric calcites with highly variable δ13C and relatively invariant δ18O. High carbon isotope values in these deposits are associated with the effects of recrystallization and rapid outgassing of CO2 during precipitation. Mg/Ca and Sr/Ca ratios differ between primary and secondary calcite speleothems, aiding their identification. Carbon and oxygen isotope values in primary calcite reflect the proportion of C3 and C4 vegetation in the local environment and the oxygen isotope composition of rainfall. Primary calcite speleothems preserve the pristine geochemical signals vital for ongoing paleoenvironmental and geochronological research. © 2009 Wiley Periodicals, Inc.  相似文献   

3.
《Gondwana Research》2001,4(3):377-386
The Kerala Khondalite belt is a Proterozoic metasupracrustal granulite facies terrain in southern India comprising garnet-biotite gneiss, garnet-sillimanite gneiss and orthopyroxene granulites as major rock types. Calc-silicate rocks and marbles, occurring as minor lithologies in the Kerala Khondalite Belt, show different mineral assemblages and reaction histories of which indicate a metamorphic P-T-fluid history dominated by internal fluid buffering during the peak metamorphism, followed by external fluid influx during decompression. The carbon and oxygen isotopic compositions of calcite from three representative metacarbonate localities show contrasting evolutionary trends. The Ambasamudram marbles exhibit carbon and oxygen isotope ratios (δ13C ∼ 0‰ and δ18O ∼ 20‰) typical of middle to late Proterozoic marine carbonate sediments with minor variation ascribed to the isotopic exchange due to the devolatilization reactions. The δ13C and δ18O values of ∼ −9‰ and 11‰, respectively, for calcite from calc-silicate rocks at Nuliyam are considerably low and heterogeneous. The wollastonite formation here, possibly corresponds to an earlier event of fluid infiltration during prograde to peak metamorphism, which resulted in decarbonation and isotope resetting. Further, petrologic evidence supports a model of late carbonic fluid infiltration that has partially affected the calc-silicate rocks, with subsequent isotope resetting, more towards the contact between calc-silicate rock and charnockite. At Korani, only oxygen isotopes have been significantly lowered (δ18O ∼ 13‰) and the process involved might be a combination of metamorphic devolatilization accompanied by an aqueous fluid influx, supported by petrologic evidence. The stable isotope signatures obtained from the individual localities, thus indicate heterogeneous patterns of fluid evolution history within the same crustal segment.  相似文献   

4.
The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ13C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ18O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ18O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ13C ? 6-8‰.  相似文献   

5.
We derive equations describing the evolution of the carbon and oxygen isotope composition of the bicarbonate in a calcite precipitating solution on the surface of a stalagmite using a classical Rayleigh approach. The combined effects of calcite precipitation, degassing of CO2 and the buffering effect of the water reservoir are taken into account. Whereas δ13C shows a progressive increase to a final constant value, δ18O shows an initial isotopic enrichment, which exponentially decays due to the buffering effect of the water reservoir. The calculated evolution is significantly different for both carbon and oxygen isotopes than derived in a recent paper [Dreybrodt W. (2008) Evolution of the isotopic composition of carbon and oxygen in a calcite precipitating H2O-CO2-CaCO3 solution and the related isotopic composition of calcite in stalagmites. Geochim. Cosmochim. Acta72, 4712-4724.].Furthermore, we discuss the isotopic evolution of the bicarbonate in the solution for long residence times on the stalagmite surface, i.e., for t→∞. The equilibrium isotope ratio of the bicarbonate is then determined by isotopic exchange between the cave atmosphere and the bicarbonate in the solution and can be calculated by equilibrium isotope fractionation. For strongly ventilated caves exchange with the cave atmosphere will result in higher δ13C and δ18O values than those observed in a pure Rayleigh distillation scenario, for sparsely ventilated caves it will result in lower δ13C and δ18O values.  相似文献   

6.
We discuss the nature of the ore-forming hydrothermal fluid in the Noya gold-bearing calcite-quartz-adularia veins of central Kyushu, Japan on the basis of oxygen, carbon, and strontium isotope ratios, and aqueous speciation calculations for the present-day geothermal fluid. The isotopic values of the Noya ore-forming fluid were estimated to be −6.5‰ for δ13C and −7.5‰ for δ18O. The oxygen isotopic equilibrium temperatures for vein calcite are more than 180°C at the bottom of the Noya mineralization zone, and decrease with increasing elevation. As the temperature decreased, the dominant carbon species in the fluid changed from H2CO3 to HCO3- at about 120°C. The equilibrium temperatures for vein quartz are consistent with the calcite calculations. The carbon and oxygen isotope trends of the Noya vein calcite and the isotope ratios of strontium suggest that the fluids that precipitated the Noya veins were controlled by an andesite-dominated geology. Chondrite-normalized REE patterns for the white-colored veins from wells 51-WT-1 and 51-WT-2 displayed a light REE-rich pattern with positive Eu anomalies, suggesting the existence of a reducing environment for the fluid. The pyrite-rich gray-colored veins and a silicified rock from well 51-WT-2 showed higher REE concentrations than did the white veins. Altered host andesitic rocks have similar REE patterns to that of the silicified rock, and have higher REE contents than the others in the drill cores. Aqueous speciation calculations showed that the fluid in the hydrothermal reservoir is currently in muscovite stability. The fluid at the ore-mineralization stage may have contained more potassium or have had a higher pH, so that adularia precipitated with calcite and quartz, as well as gold. Fluid boiling at depth in the system produced the gold-bearing calcite-quartz-adularia veins.  相似文献   

7.
The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ18OSMOW=+24.4 to +26.5‰δ13CPDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ18OSMOW=+18.4 to +25.8‰; δ13CPDB=?2.1 to +0.2‰), and calcite (δ18OSMOW=+21.3 to +32.6‰; δ13CPDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ18O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ18O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.  相似文献   

8.
The clay fractions of sedimentary kaolin deposits representing different ages (Carboniferous and Cretaceous), types (pisolitic flint and plastic), and localities (Sinai and Aswan) from Egypt were analyzed for their H and O isotopic compositions to examine the paleoclimate conditions during their formation. The δD values of the Carboniferous deposits in Sinai range between −67‰ and −88‰, while the values for the Cretaceous deposits in Sinai range between −59‰ and −75‰. The δ18O values of the Carboniferous deposits range from 17.9‰ to 19.4‰ and the values for the Cretaceous deposits range between 19.2‰ and 20.4‰. The relatively low δD and δ18O values of the Carboniferous deposit at the Abu Natash area (−67‰ and 17.9‰, respectively) compared to other Carboniferous deposits (averages of −83.3‰, and 18.8‰ for δD and δ18O, respectively) could be due to isotopic exchange between this deposit and the adjacent dolomite and/or the enclosed hydrothermally-formed Mn ores of the Carboniferous Um Bogma Formation. The δD and δ18O values of the Cretaceous pisolitic flint kaolin deposit from Aswan (averages of −65‰ and 20.3‰, respectively) and plastic kaolin from the same area (averages of −66‰ and 19.5‰, respectively) are almost identical. The differences in the δ18O values between the clay fractions of the pisolitic flint kaolin (20.3‰) and the previously analyzed bulk kaolin of the same deposit (average of 17.5‰) suggest a significant effect of non-clay minerals on the isotopic compositions of the kaolin deposits.The H and O isotopic compositions plot close to the kaolinite line that marks the isotopic composition of kaolinite in equilibrium with meteoric water at 20 °C. This indicates that the kaolinite from both the Carboniferous and Cretaceous deposits in Egypt formed by meteoric water weathering of the source rock(s). The δD and δ18O values also suggest that kaolinite of these deposits formed under warm-temperate to tropical conditions. The slight deviations of some samples from the kaolinite line suggest post-depositional modifications of the isotopic compositions of studied deposits probably due to the interaction between earlier-formed kaolinite and downward percolating meteoric water.The δD and δ18O values of the Cretaceous and Carboniferous deposits from all localities suggest that both deposits formed under similar climatic conditions due to the location of Egypt at almost the same distance from the equator either to the south during the Carboniferous or to the north during the Cretaceous.  相似文献   

9.
Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.  相似文献   

10.
UWE BRAND 《Sedimentology》1982,29(1):139-147
The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ18O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ18O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ18O and δ13C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ18O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ13C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.  相似文献   

11.
The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ18O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ18O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ18O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ18O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ18O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ18O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ18O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ18O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.  相似文献   

12.
《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   

13.
The intracrystalline diffusion rate of oxygen in diopside was constrained based on natural isotopic variations from a granulite facies marble from Cascade Slide, Adirondacks (New York, USA). The oxygen isotope compositions of the diopsides, measured as a function of grain size, are nearly constant (20.9 ± 0.3‰ vs. SMOW) over the entire measured size range (0.3–3.2 mm diameter). The δ18O values of the cores of calcite grains are 23.0‰. Temperature estimates based on the Δ18O(calcite-diopside) are 800d?C, in agreement with the highest previous thermometric estimates for these rocks. The lack of isotopic variation in the diopsides as a function of grain size requires that the oxygen intracrystalline diffusion rate in diopside from the Adirondack samples was very slow. The maximum diffusion rates (D800d?C parallel to the c-axis) were calculated with an infinite reservoir model (IRM) and a finite reservoir model (FRM) that incorporates mineral modal abundances and initial isotopic variations. For an assumed activation energy (Q) = 100 kJ/mol, the IRM diffusion rate estimate of 1.6 times 10-20cm2/s is two orders of magnitude faster than from the FRM; at Q=500kJ/mol, the D800d?C estimate for both methods is c. 5.6 times 10-20 cm2/s. The present results require that a hydrothermal fluid significantly enhances the diffusion rate of oxygen in diopside if previous data are correct. The δ18O(SMOW) and δ13C(PDB) values of the calcite, measured in situ with a CO2 laser, are 22.9 ± 0.3, 0.1±0.3‰ in the grain cores, 22.1 ±0.3, 0.2 ±0.1‰ at the grain boundaries and 21.7 ±0.4, -0.6±0.1‰ abutting diopside grains. The δ18O and δ13δC values measured conventionally are: crystal cores, 22.96, -0.95‰; abutting diopside grains, 22.38, -0.93‰; bulk, 22.79, -0.95%. Use of the bulk δ18O(calcite) values for thermometry yields unreasonably high temperatures. The lower δ18O values at the calcite grain boundaries are not due to retrograde diffusional exchange with the diopside, they are thought to be a result of a late retrograde fluid infiltration.  相似文献   

14.
《Quaternary Science Reviews》2007,26(11-12):1670-1689
Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the 13C and 18O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ18O values ranging between −6.5‰ and 28‰ VSMOW and δ13C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ13C and δ18O range, suggesting that their environmental setting and the mechanism by which they formed controls their 13C and 18O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ13C value that is in equilibrium with that of the parent water, while its δ18O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ18O and calcite saturation state of the parent water. By contrast, the δ18O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ13C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ18O and δ13C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.  相似文献   

15.
碳酸盐矿物是火山岩储层内重要的矿物成分,长岭断陷火山岩储层内的自生碳酸盐矿物主要是方解石.本文通过对营城组储层内方解石矿物的碳氧同位素特征分析,探讨储层内碳酸盐矿物成因.研究表明,长岭断陷火山岩储层内方解石δ13 CV-PDB值范围为-12.7‰～0.4‰,δ18OV-SMOw值范围为3.8‰～12‰,具有高δ18O值.与方解石平衡的CO2碳同位素计算值范围较宽,为-16.0‰～2.2‰,表明其形成物质的多源性.在δ18 O-δ13C图解中显示,形成碳酸盐矿物的CO2来源于幔源-岩浆无机成因的CO2和有机质演化过程中产生的CO2,以无机成因CO2源为主.这些无机成因CO2、有机成因CO2和沉积有机质热演化产生的有机酸溶于流体,形成酸性流体.火山岩储层中碳酸盐矿物的形成实质就是这种酸性流体与储层围岩反应的结果.  相似文献   

16.
《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   

17.
The Valentine wollastonite skarn in the north-west Adirondack Mountains, New York, is a seven million ton deposit which resulted from channellized infiltration of H2O-rich, silica-bearing fluids. The wollastonite formed by reaction of these fluids with non-siliceous calcite marble. The skarn formed at the contact of the syenitic Diana Complex and was subsequently overprinted by Grenville-age granulite facies metamorphism and retrograde hydrothermal alteration during uplift. Calcite marbles adjacent to the deposit have generally high δ18O values (c. 21‰), typical of Grenville marbles which have not exchanged extensively with externally derived fluids. Carbon isotopic fractiona-tions between coexisting calcite and graphite in the marbles indicate equilibration at 675d? C, consistent with the conditions of regional metamorphism. Oxygen isotopic ratios from wollastonite skarn are lower than in the marbles and show a 14‰ variation (-1‰ to 13‰). Some isotopic heterogeneity is preserved from skarn formation, and some represents localized exchange with low-δ18O retrograde fluids. Detailed millimetre- to centimetre-scale isotopic profiles taken across skarn/marble contacts reveal steep δ18O gradients in the skarn, with values increasing towards the marble. The gradients reflect isotopic evolution of the fluid as it reacted with high δ18O calcite to form wollastonite. Calcite in the marble preserves high δ18O values to within <5 mm of the skarn contact. The preservation of high δ18O values in marbles at skarn contacts and the disequilibrium fractionation between wollastonite skarn and calcite marble across these contacts indicate that the marbles were not infiltrated with significant quantities of the fluid. Thus, the marbles were relatively impermeable during both the skarn formation and retrograde alteration. Skarn formation may have been episodic and fluid flow was either chaotic or dominantly parallel to lithological contacts. Although these steep isotope gradients resemble fluid infiltration fronts, they actually represent the sides of the major flow system. Because chromatographic infiltration models of mass transport require the assumption of pervasive fluid flow through a permeable rock, such models are not applicable to this hydrothermal system and, by extension, to many other metamorphic systems where low-permeability rocks restrict fluid migration pathways. Minimum time-integrated fluid fluxes have been calculated at the Valentine deposit using oxygen isotopic mass balance, reaction progress of fluid buffering reactions, and silica mass balance. All three approaches show that large volumes of fluid were necessary to produce the skarn, but silica mass balance calculations yield the largest minimum flux and are hence the most realistic.  相似文献   

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

19.
The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ13C = ?15.51 to ?5.1‰, δ18O = +3.6 to +22.5‰. δ13C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ34S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ34S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.  相似文献   

20.
Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ18O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ18O and δD values of stalagmites deposited during peak interglacials vary between ?8 and ?4 ‰ (VPDB) and ?53 and ?20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from ?2.6 to ?1.1‰ in δ18O (VPDB) and ?7.6 and ?3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.  相似文献   

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