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1.
The stable carbon and oxygen isotope compositions of fossil ostracods are powerful tools to estimate past environmental and climatic conditions. The basis for such interpretations is that the calcite of the valves reflects the isotopic composition of water and its temperature of formation. However, calcite of ostracods is known not to form in isotopic equilibrium with water and different species may have different offsets from inorganic precipitates of calcite formed under the same conditions. To estimate the fractionation during ostracod valve calcification, the oxygen and carbon isotope compositions of 15 species living in Lake Geneva were related to their autoecology and the environmental parameters measured during their growth. The results indicate that: (1) Oxygen isotope fractionation is similar for all species of Candoninae with an enrichment in 18O of more than 3‰ relative to equilibrium values for inorganic calcite. Oxygen isotope fractionation for Cytheroidea is less discriminative relative to the heavy oxygen, with enrichments in 18O for these species of 1.7 to 2.3‰. Oxygen isotope fractionations for Cyprididae are in-between those of Candoninae and Cytheroidea. The difference in oxygen isotope fractionation between ostracods and inorganic calcite has been interpreted as resulting from a vital effect. (2) Comparison with previous work suggests that oxygen isotope fractionation may depend on the total and relative ion content of water. (3) Carbon isotope compositions of ostracod valves are generally in equilibrium with DIC. The specimens’ δ13C values are mainly controlled by seasonal variations in δ13CDIC of bottom water or variation thereof in sediment pore water. (4) Incomplete valve calcification has an effect on carbon and oxygen isotope compositions of ostracod valves. Preferential incorporation of at the beginning of valve calcification may explain this effect. (5) Results presented here as well as results from synthetic carbonate growth indicate that different growth rates or low pH within the calcification site cannot be the cause of oxygen isotope ‘vital effects’ in ostracods. Two mechanisms that might enrich the 18O of ostracod valves are deprotonation of that may also contribute to valve calcification, and effects comparable to salt effects with high concentrations of Ca and/or Mg within the calcification site that may also cause a higher temperature dependency of oxygen isotope fractionation.  相似文献   

2.
《Quaternary Science Reviews》2007,26(9-10):1332-1343
The growth of a well-dated stalagmite from Barbados records high infiltration rates into the karst aquifer and hence increased rainfall intensity between 6.7 and 3 ka BP in agreement with records from Lake Miragoane, Haiti [Hodell et al., 1991. Reconstruction of the Caribbean climate change over the past 10,500 years. Nature 352, 790–793], mainly reflecting the insolation maximum of the Northern Hemisphere. Both the lake record and the stable isotope record of the stalagmite reveal additional centennial variability of recharge. High oxygen isotope values in stalagmite calcite, corresponding to reduced recharge, are synchronous with periods of lower stable isotope values recorded in Lake Miragoane ostracods, previously attributed to enhanced precipitation. Accordingly, periods of increased recharge in Barbados correspond to 18O-enriched isotope values of ostracods, which were attributed to higher evaporation/precipitation ratios in the lakes. We ascribe this apparent discrepancy to changes in seasonality, i.e., winter periods of reduced temperature and relative humidity following summer months of increased precipitation. At present, such climate conditions occur during periods of enhanced Northern Atlantic Oscillation (NAO+). If enhanced seasonality is a consequence of a NAO+ situation, the apparent discrepancy of high isotope values in lakes (previously attributed to droughts) can be reconciled with lower winter temperatures in the lakes. Further, the correlation of solar intensity (derived from 14C and 10Be) with the isotopic signals recorded in the lacustrine sediments suggests a solar forcing of the NAO during the mid Holocene.  相似文献   

3.
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   

4.
Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ13C) and oxygen (δ18O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO2 degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ13C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO2 degassing and tufa precipitation rate downstream. The Δ13C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous 12CO2 degassing downstream leaving the carbon pool enriched in 13C. In the case of oxygen, the isotope fractionation (Δ18O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ18O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ18O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.  相似文献   

5.
Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ18O and ±0.71‰ for δ13C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ18O and 0.10-0.29‰ for δ13C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ13C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ13C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ18O (up to 9.4‰), intercrystalline inhomogeneity in δ18O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ18O and δ13C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ18O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ18O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.  相似文献   

6.
The calcium isotopic compositions (δ44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (αs−f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of αs−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ44Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.  相似文献   

7.
Variations in the isotopic composition of Fe in Late Archean to Early Proterozoic Banded Iron Formations (BIFs) from the Transvaal Supergroup, South Africa, span nearly the entire range yet measured on Earth, from –2.5 to +1.0‰ in 56Fe/54Fe ratios relative to the bulk Earth. With a current state-of-the-art precision of ±0.05‰ for the 56Fe/54Fe ratio, this range is 70 times analytical error, demonstrating that significant Fe isotope variations can be preserved in ancient rocks. Significant variation in Fe isotope compositions of rocks and minerals appears to be restricted to chemically precipitated sediments, and the range measured for BIFs stands in marked contrast to the isotopic homogeneity of igneous rocks, which have δ56Fe=0.00±0.05‰, as well as the majority of modern loess, aerosols, riverine loads, marine sediments, and Proterozoic shales. The Fe isotope compositions of hematite, magnetite, Fe carbonate, and pyrite measured in BIFs appears to reflect a combination of (1) mineral-specific equilibrium isotope fractionation, (2) variations in the isotope compositions of the fluids from which they were precipitated, and (3) the effects of metabolic processing of Fe by bacteria. For minerals that may have been in isotopic equilibrium during initial precipitation or early diagenesis, the relative order of δ56Fe values appears to decrease in the order magnetite > siderite > ankerite, similar to that estimated from spectroscopic data, although the measured isotopic differences are much smaller than those predicted at low temperature. In combination with on-going experimental determinations of equilibrium Fe isotope fractionation factors, the data for BIF minerals place additional constraints on the equilibrium Fe isotope fractionation factors for the system Fe(III)–Fe(II)–hematite–magnetite–Fe carbonate. δ56Fe values for pyrite are the lowest yet measured for natural minerals, and stand in marked contrast to the high δ56Fe values that are predicted from spectroscopic data. Some samples contain hematite and magnetite and have positive δ56Fe values; these seem best explained through production of high 56Fe/54Fe reservoirs by photosynthetic Fe oxidation. It is not yet clear if the low δ56Fe values measured for some oxides, as well as Fe carbonates, reflect biologic processes, or inorganic precipitation from low-δ56Fe ferrous-Fe-rich fluids. However, the present results demonstrate the great potential for Fe isotopes in tracing the geochemical cycling of Fe, and highlight the need for an extensive experimental program for determining equilibrium Fe isotope fractionation factors for minerals and fluids that are pertinent to sedimentary environments.  相似文献   

8.
Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42− and Cl− salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor αFe(III)aq-Fe(II)aq ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9‰ (αFe(III)aq-Fe(II)aq ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.  相似文献   

9.
Stable carbon isotope (δ13C) analysis was used in the Peridido Estuary, Florida U.S. to determine the predominant carbon source that supports the bacterial assemblage. Stable carbon isotope values were measured in the suspended particulate matter (SPM), dissolved organic and inorganic matter, and bacteria. Stable nitrogen isotope (δ15N) ratios were measured in SPM and nitrate to assist in understanding carbon cycling through the estuary. Analyses were conducted on samples from riverine, coastal, and anthropogenic sources and compared with samples from the bay. Stable isotope ratio analysis was coupled with estimates of mixing of riverine and coastal waters into the bay. Preliminary observation of the °13C data indicates that terrestrial organic matter is the primary carbon source that is assimilated by bacteria in the ecosystem. Stable isotope data from carbon and nitrogen pools in combination with analysis of estuarine current velocities indicates that primary production is an important factor in the carbon cycle. This study demonstrates the importance of stable isotope analysis of multiple carbon and nitrogen pols to assess sources and cycling of organic matter.  相似文献   

10.
Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ18O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ18O line with δD values that are almost 50‰ lower. The δD-δ18O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.  相似文献   

11.
The stable carbon isotope (δ13C) and elemental C/N ratios in Total Organic Carbon (TOC) extracted from radiometrically dated cores from two Midwestern USA lakes were determined to investigate the factors that control these values in temperate lakes. The range of δ13C values (-26 to -32%) and C/N ratios (mean value ∼10.8) are typical of values reported for other temperate lake organic matter in this region. In the core from Lake Winnebago, Wisconsin, a negative correlation was seen between the TOC and δ13C, which can be interpreted in terms of a re-mixing and consumption of sedimented organic carbon along with rapid equilibration throughout the water column. No correlation was seen between the TOC and δ13C in the record from Ladd Lake, Ohio, implying that in this latter lake productivity alone was not a singular process controlling the isotope ratio. Here, it is suggested that equilibrium conditions are maintained such that the DIC of the water is never depleted of aqueous CO2 during high organic production and the resulting δ13C of the organic carbon lacks correlation with the TOC. Further, in this lake a fine resolution analysis was carried out which indicated a possible anthropogenic influence on the isotope ratio around times when human settlement (∼300 yrs ago) and enhanced agricultural practices (∼80 yrs ago) were significant. The study shows that carbon isotope studies are useful in paleolimnologic investigations.  相似文献   

12.
Stable isotope ratios from tree rings and peatland mosses have become important proxies of past climate variations. We here compare recent stable carbon and oxygen isotope ratios in cellulose of tree rings from white spruce (Picea glauca), growing near the arctic tree line; and cellulose of Sphagnum fuscum stems, growing in a hummock of a subarctic peatland, in west-central Canada. Results show that carbon isotopes in S. fuscum correlate significantly with July temperatures over the past ~20 yr. The oxygen isotopes correlate with both summer temperature and precipitation. Analyses of the tree-ring isotopes revealed summer temperatures to be the main controlling factor for carbon isotope variations, whereas tree-ring oxygen isotope ratios are controlled by a combination of spring temperatures and precipitation totals. We also explore the potential of combining high-frequency (annual) climate signals derived from long tree-ring series with low-frequency (decadal to centennial) climate signals derived from the moss remains in peat deposits. This cross-archive comparison revealed no association between the oxygen isotopes, which likely results from the varying sensitivity of the archives to different seasons. For the carbon isotopes, common variance could be achieved through adjustments of the Sphagnum age model within dating error.  相似文献   

13.
Mg isotope ratios (26Mg/24Mg) are reported in soil pore-fluids, rain and seawater, grass and smectite from a 90 kyr old soil, developed on an uplifted marine terrace from Santa Cruz, California. Rain water has an invariant 26Mg/24Mg ratio (expressed as δ26Mg) at −0.79 ± 0.05‰, identical to seawater δ26Mg. Detrital smectite (from the base of the soil profile, and therefore unweathered) has a δ26Mg value of 0.11‰, potentially enriched in 26Mg by up to 0.3‰ compared to the bulk silicate Earth Mg isotope composition (although within the range of all terrestrial silicates). The soil pore-waters show a continuous profile with depth for δ26Mg, ranging from −0.99‰ near the surface to −0.43‰ at the base of the profile. Shallow pore-waters (<1 m) have δ26Mg values that are similar to, or slightly lower than the rain waters. This implies that the degree of biological cycling of Mg in the pore-waters is relatively small and is quantified as <32%, calculated using the average Mg isotope enrichment factor between grass and rain (δ26Mggrass-δ26Mgrain) of 0.21‰. The deep pore-waters (1-15 m deep) have δ26Mg values that are intermediate between the smectite and rain, ranging from −0.76‰ to −0.43‰, and show a similar trend with depth compared to Sr isotope ratios. The similarity between Sr and Mg isotope ratios confirms that the Mg in the pore-waters can be explained by a mixture between rain and smectite derived Mg, despite the fact that Mg and Sr concentrations may be buffered by the exchangeable reservoir. However, whilst Sr isotope ratios in the pore-waters span almost the complete range between mineral and rain inputs, Mg isotopes compositions are much closer to the rain inputs. If Mg and Sr isotope ratios are controlled uniquely by a mixture, the data can be used to estimate the mineral weathering inputs to the pore-waters, by correcting for the rain inputs. This isotopic correction is compared to the commonly used chloride correction for precipitation inputs. A consistent interpretation is only possible if Mg isotope ratios are fractionated either by the precipitation of a secondary Mg bearing phase, not detected by conventional methods, or selective leaching of 24Mg from smectite. There is therefore dual control on the Mg isotopic composition of the pore-waters, mixing of two inputs with distinct isotopic compositions, modified by fractionation. The data provide (1) further evidence for Mg isotope fractionation at the surface of the Earth and (2) the first field evidence of Mg isotope fractionation during uptake by natural plants. The coherent behaviour of Mg isotope ratios in soil environments is encouraging for the development of Mg isotope ratios as a quantitative tracer of both weathering inputs of Mg to waters, and the physicochemical processes that cycle Mg, a major cation linked to the carbon cycle, during continental weathering.  相似文献   

14.
贺兰山地区树轮碳氧同位素与夏季风降水的相关性讨论   总被引：1，自引：0，他引：1  
分析了贺兰山地区油松树轮的稳定碳氧同位素组成对环境因素的响应关系 , 发现树轮碳氧同位素组成均与当年 5～ 9月总降水量具有较好的响应关系 , 碳同位素组成与 5～ 9月总降水量呈负相关关系 ,而氧同位素组成与 5～ 9月总降水量呈正相关关系 ,二者都可较好地反映该地区夏季风降水量的变化.同时 ,碳氧同位素的相关性分析表明二者具有一定程度的负相关性.树轮碳氧同位素的分馏机理十分复杂,其同位素组成不仅与降水量有关,同时还受其他环境因素的影响,单纯利用一种同位素指标来提取相应的气候信息,存在很大的不确定性.在本研究中 ,同时采用两种同位素指标来研究其气候意义 ,使得出的结论更加可靠.因此 ,夏季风降水量是控制该地区树轮稳定碳氧同位素组成的主要因素.  相似文献   

15.
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   

16.
We present the first near millennium-length, annually resolved stable isotope record from bristlecone pines (Pinus longaeva, D.K Bailey). The carbon isotope ratios from the cellulose of seven trees from the White Mountains of California, corrected for anthropogenic changes in atmospheric chemistry, are used to reconstruct growing season (June through August) precipitation back to AD 1085. Extremely negative isotope results are strongly correlated with proposed severest El Niño events over the last 500 yr, and similar values in the first half of the millennium are used to reconstruct a further 13 strong El Niño events, concentrated in the 12th Century and the mid 13th and 14th Centuries. Ring-width chronologies from adjacent sites in the White Mountains demonstrate a high degree of decadal covariance with the δ13C series, although there are several periods of notable divergence.  相似文献   

17.
The skeletal oxygen isotope ratio of Porites corals is the most frequently used proxy of past seawater temperature and composition for tropical and subtropical oceans. However, field calibration of the proxy signals is often difficult owing to the dual dependence of skeletal oxygen isotope ratio on temperature and the oxygen isotope composition of water. We conducted tank experiments in which we grew Porites spp. colonies for 142 d in thermostated seawater at five temperature settings between 21°C and 29°C under moderate light intensity of 250 μmol m−2 s−1 with a 12:12 light:dark photoperiod. A skeletal isotope microprofiling technique applied along the major growth axis of each colony revealed that the oxygen isotope ratios of newly deposited skeleton in most colonies remained almost constant during tank incubation, thus providing an ideal situation for precise calibration of oxygen isotope ratio proxy signals. However, the oxygen isotope ratios displayed an unusually large intercolony variability (∼1‰) at each temperature setting although the mean slope (∼0.15‰ °C−1) obtained for the temperature-skeletal oxygen isotope ratio relationship was close to previous results. The intercolony variations in the oxygen isotope ratios were apparently caused by kinetic isotope effects related to variations in the skeletal growth rate rather than by species-specific variability or genetic differences within species. No correlation was found between skeletal carbon isotope ratios and temperature. The carbon isotope ratios showed significantly inverse correlation with linear growth rates, suggesting a kinetic isotope control at low growth rates. Observed intercolony variability in skeletal carbon isotope ratios (∼5‰) can be partly attributed to growth-rate-related kinetic isotope effects.  相似文献   

18.
The Korneuburg Basin, with mainly upper Lower Miocene (Karpatian) sediment filling, is divided by the Mollmannsdorf–Obergänserndorf Swell into two sub-basins characterised by different environmental settings. Paleoecological data indicate a marine northern part and a mainly estuarine southern part. Nevertheless, short-termed marine ingressions from the north allowed marine faunas (ostracods, molluscs, and echinoids) to temporarily settle the southern part of the basin. The carbon and oxygen isotopic composition of gastropod shells from these different environmental settings were investigated. Highest δ18O and δ13C values are found in Turritella shells from the northern part of the basin, and in Turritella shells from layers interpreted as a marine ingression in the south. Generally, components of the mudflat fauna (Tympanotonos cinctus, Granulolabium bicinctum, Terebralia bidendata, and Ocenebra crassilabiata) have slightly lower isotope values. Considerable freshwater influx in the southern part is documented by abundant freshwater genera such as Melanopsis, which show low carbon and oxygen isotope values. Data of identical taxa, especially Turritella and Granulolabium, reflect a trend from higher isotope values at the marine northern part to slightly lower values in the mainly estuarine southern part of the basin. Differences in δ18O between the marine and the estuarine assemblages are interpreted to be caused by changes in salinity and isotopic composition of ambient water rather than by temperature. Paleotemperature estimates derived from oxygen isotope data are in good agreement with existing paleoclimatic proxies for the Korneuburg Basin. Hence, an annual range of the sea-surface temperature from 13 to 26°C can be predicted within that protected basin.  相似文献   

19.
The Albian-Danian limestones of Cauvery Basin show a wide range of d13C and d18O values (–13.2 to +1.1% and –9.0 to –2.5%, respectively). The cement samples show negative carbon and oxygen isotope values (–18.9 to –3.9% and –9.0 to –4.3%, respectively). The petrographic study reveals the presence of algae, molluscs, bryozoans, foraminifers and ostracods as major framework constituents. The limestones have microspar and equant sparry calcite cements. The pore spaces and vugs are filled with sparry calcite cement. The bivariate plot of d13C and d18O suggests that most of the samples fall in the freshwater limestone and meteoric field, while few samples fall in the marine limestone and soil calcite fields. The presence of sparry calcite cement, together with negative carbon and oxygen isotope values, indicates that these limestones have undergone meteoric diagenesis.  相似文献   

20.
To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:
1.
Oxygen isotope exchange between [CO3]2− and H2O:
(1)  相似文献   

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