首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 46 毫秒
1.
The apparent inconsistency in calcite-water fractionation does occur between the arithmetic combination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta67, 387-399] and the experimental determination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Mineral90, 1121-1130]. To resolve this issue is to acknowledge whether or not the isotope salt effect of dissolved minerals would occur on oxygen isotope exchange between water and the minerals of interest. The question is whether or not a term of mineral-water interaction should be taken into account when calculating mineral-water 103ln α factors by an arithmetic combination between theoretical 103ln β factors for mineral and water, respectively. The hydrothermal experiments of Hu and Clayton [Hu G.-X., and Clayton R.N. (2003) Oxygen isotope salt effects at high pressure and high temperature, and the calibration of oxygen isotope geothermometers. Geochim. Cosmochim. Acta67, 3227-3246] demonstrate the absence of isotope salt effect on the oxygen isotope fractionation between calcite and water, and this abnormal behavior reasonably explains the so-called inconsistency in the calcite-water fractionations of Zhou and Zheng (2003, 2005). We argue that the mineral-water correction is still necessary for calculation of fractionations in mineral-water systems. New experimental data for oxygen isotope fractionations involving dolomite and cerussite are consistent with the calculations of Zheng [Zheng Y.-F. (1999a) Oxygen isotope fractionation in carbonate and sulfate minerals. Geochem. J.33, 109-126], but also shed light on the assumptions used in modifying the increment method. We argue that the modified increment method has developed into a theoretical mean of predictive power for calculation of oxygen isotope fractionation factors for crystalline minerals of geochemical interest.  相似文献   

2.
A compilation of 18O analyses of minerals separated from about 400 igneous and metamorphic rocks from published investigations reveals regularity in the fractionation of 18O among associated minerals, suggesting that an approach to isotopic equilibrium may be common. However, for only a minority of terrestrial rocks are these regularities sufficiently systematic to be compatible with the actual attainment and preservation of isotopic equilibrium among three minerals. Fractionations among triplets of quartz, calcite, feldspar, muscovite, and magnetite show some correspondence to those expected on the basis of experimental calibrations; however, there are also considerable deviations. The variability of natural data is such that less than half of the rocks analyzed to date would yield concordant 18O-derived temperatures. Of the additional 52 mineral triplets studied, plagioclase-pyrox-ene-ilmenite, plagioclase-pyroxene-magnetite, plagioclase-pyroxene-olivine, quartz-amphibole-garnet, pyroxene-ilmenite-magnetite, muscovite-biotite-magnetite, and quartz-muscovite-amphibole show the most systematic oxygen isotope fractionations. For 12 other mineral triplets a defined isotope fractionation relationship may be postulated to underlie the data; however for these a close approach to isotopic equilibrium is not commonly observed. For 33 of the mineral triplets an approach to isotopic equilibrium can be noted; however, the scatter of the available data is such that a systematic influence of a factor, such as temperature, on the size of the 18O fractionation could not be detected. In the past, regularities of oxygen isotope fractionations among three minerals have been used to establish secondary isotope geothermometers. Before this can be done with any reliability, however, the effects of possible retrograde isotope exchange and spurious correlation must be accounted for.  相似文献   

3.
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   

4.
Isotopic fractionation factors for oxygen, hydrogen and silicon have been calculated using first-principles methods for the kaolinite, quartz, water (ice and gas water) system. Good agreement between theory and experiment is obtained for mineral-water oxygen isotope fractionation. This approach gives reliable results on isotopic fractionation factors as a function of temperature, within a relative precision of typically 5%. These calculations provide independent quantitative constraints on the internal fractionation of oxygen in kaolinite, the fractionation of silicon isotopes at equilibrium, or hydrogen fractionation between kaolinite and water. Calculated fractionation factors at 300 K are 12.5‰ for the kaolinite internal-fractionation of oxygen, and 1.6‰ for silicon fractionation between quartz and kaolinite.  相似文献   

5.
Oxygen isotopic compositions of silicate inclusions in IVA iron meteorites have been measured with an in situ UV laser microprobe technique. The homogeneity of oxygen isotopic compositions within and among individual mineral grains has also been examined. Oxygen isotope fractionations between coexisting mineral pairs were utilized in oxygen isotope thermometry. Our measured Δ17O values, ranging from 0.97 to 1.25‰, are characteristic of a single reservoir and fully confirm the oxygen isotopic similarity between IVA irons and L/LL chondrites. Steinbach and São João Nepomuceno, containing inclusions of two silicate minerals in mutual contact, exhibit a mass-dependent fractionation of 18O/16O between tridymite and bronzite with apparent oxygen isotopic heterogeneity. The SiO2-bearing member, Gibeon, gives homogeneous oxygen isotopic compositions without detectable fractionation of 18O/16O between tridymite and quartz. Oxygen isotope equilibrium temperatures are estimated for coexisting tridymite and bronzite in the same sample slabs or clusters in Steinbach and São João Nepomuceno. The fractionations of 18O/16O between bronzite and tridymite range from 1.6 to 2.3‰ in different sample slabs or clusters. On the basis of the closure temperature concept, cooling rates are estimated at approximately 20 to 1000°C/Myr between 800 and 1000°C, a range of temperatures not accessible to other cooling rate methods. Using the Fast Grain Boundary diffusion model, we have demonstrated that significant oxygen heterogeneity both in tridymite and bronzite is probably due to isotope exchange during cooling between minerals with various grain sizes and mineral abundances in different regions of the samples. The new estimates of cooling rate by oxygen isotope thermometry refine previous cooling curves of IVA irons and support the breakup-reassembly model for the IVA parent body.  相似文献   

6.
Phosphoric acid digestion has been used for oxygen- and carbon-isotope analysis of carbonate minerals since 1950, and was recently established as a method for carbonate ‘clumped isotope’ analysis. The CO2 recovered from this reaction has an oxygen isotope composition substantially different from reactant carbonate, by an amount that varies with temperature of reaction and carbonate chemistry. Here, we present a theoretical model of the kinetic isotope effects associated with phosphoric acid digestion of carbonates, based on structural arguments that the key step in the reaction is disproportionation of H2CO3 reaction intermediary. We test that model against previous experimental constraints on the magnitudes and temperature dependences of these oxygen isotope fractionations, and against new experimental determinations of the fractionation of 13C-18O-containing isotopologues (‘clumped’ isotopic species). Our model predicts that the isotope fractionations associated with phosphoric acid digestion of carbonates at 25 °C are 10.72‰, 0.220‰, 0.137‰, 0.593‰ for, respectively, 18O/16O ratios (1000 lnα∗) and three indices that measure proportions of multiply-substituted isotopologues . We also predict that oxygen isotope fractionations follow the mass dependence exponent, λ of 0.5281 (where ). These predictions compare favorably to independent experimental constraints for phosphoric acid digestion of calcite, including our new data for fractionations of 13C-18O bonds (the measured change in Δ47 = 0.23‰) during phosphoric acid digestion of calcite at 25 °C.We have also attempted to evaluate the effect of carbonate cation compositions on phosphoric acid digestion fractionations using cluster models in which disproportionating H2CO3 interacts with adjacent cations. These models underestimate the magnitude of isotope fractionations and so must be regarded as unsucsessful, but do reproduce the general trend of variations and temperature dependences of oxygen isotope acid digestion fractionations among different carbonate minerals. We suggest these results present a useful starting point for future, more sophisticated models of the reacting carbonate/acid interface. Examinations of these theoretical predictions and available experimental data suggest cation radius is the most important factor governing the variations of isotope fractionation among different carbonate minerals. We predict a negative correlation between acid digestion fractionation of oxygen isotopes and of 13C-18O doubly-substituted isotopologues, and use this relationship to estimate the acid digestion fractionation of for different carbonate minerals. Combined with previous theoretical evaluations of 13C-18O clumping effects in carbonate minerals, this enables us to predict the temperature calibration relationship for different carbonate clumped isotope thermometers (witherite, calcite, aragonite, dolomite and magnesite), and to compare these predictions with available experimental determinations. The success of our models in capturing several of the features of isotope fractionation during acid digestion supports our hypothesis that phosphoric acid digestion of carbonate minerals involves disproportionation of transition state structures containing H2CO3.  相似文献   

7.
碳酸盐矿物氧同位素分馏的理论研究   总被引：13，自引：2，他引：13  
应用增量方法系统地计算了碳酸盐矿物的同位素分馏系数，得到不同结构和成分的碳酸盐矿物的18O富集顺序为：菱铁矿〉铁白云石〉菱镁矿≥白云石≥方解石〉文石〉菱锶矿〉白铅矿〉碳钡矿。在0℃～1200℃范围内获得了一组内部一致的碳酸盐－水体系的理论分馏系数，这些计算结果与已知的实验和／或经验数据之间存在良好的一致性，因此本文对碳酸盐矿物氧同位素分馏系数的理论校准不仅可应用于共生矿物组合形成温度的确定，而且能够应用于其形成机理的示踪。 计算结果表明，白云石的氧同位素分馏行为与方解石相似，在25℃下白云石与方解石之间的平衡分馏为0.56‰ 。理论预测文石相对于方解石显著地亏损 δ18O，在25℃时方解石与文石之问的平衡分馏为4.47‰ 。文石向方解石的同质多相转变可能是通过一种没有同位素再造的惰性氧结构单元[CO3]2- 进行的，即只涉及Ca2+ 与[C03]2- 基团之间键的断裂和再组台而未出现[CO3]2- 基团内部C－O键的断裂和再组合。结果在自然界和实验室实验中，文石中氧同位索配分的温度关系能够传递副方解石中来。这种在同质多相转变形成方解石过程中的氧同位素继承性对于了解白云石－方解石－水体系分馏的难题至关重要。理论预测也能够用来解释对方解石分馏的经验估算与实验测定之间的分歧。  相似文献   

8.
Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO3 minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.  相似文献   

9.
Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in 56Fe/54Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ56FeFe(OH)3-Fe(II)aq fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.  相似文献   

10.
高温下非传统稳定同位素分馏   总被引：5，自引：1，他引：4  
黄方 《岩石学报》2011,27(2):365-382
过去十几年来,非传统稳定同位素地球化学在高温地质过程的研究中取得了的重大进展。多接收诱导耦合等离子质谱(MC-ICP-MS)的应用引发了稳定同位素分析方法的重大突破,使得精确测定重元素的同位素比值成为可能。本文总结了以Li、Fe和Mg同位素为代表的非传统稳定同位素在岩石地球化学研究中的应用。Li同位素目前被广泛地用于地幔地球化学、俯冲带物质再循环和变质作用的研究中,可以用来示踪岩浆的源区性质和扩散等动力学过程。不同价态的Fe在矿物熔体相之间的分配可以产生Fe同位素分馏,可以发生在地幔交代、部分熔融、分离结晶等过程中。岩浆岩的Mg同位素则大致反映其源区的特征,地幔的Mg同位素组成比较均一,这为研究低温地球化学过程中Mg同位素的分馏提供一个均一的背景。此外,Cl,Si,Cu,Ca,U等等同位素体系也具有广阔的应用前景。对同位素分馏机制的实验研究和理论模拟为理解非传统稳定同位素数据提供了必要的指导。实验表明,高温下具有不同的迁移速度的轻、重同位素可以产生显著的动力学同位素分馏,这一分馏可以在化学扩散、蒸发和凝华等过程中发生;同位素在矿物和熔体以及流体相中化学环境的差异使得不同相之间可以发生平衡分馏。而最近的硅酸盐岩浆的热扩散和热迁移实验则揭示了一种"新"的岩浆分异和同位素分馏机制。沿着温度梯度,硅酸盐岩浆可以发生显著的元素和同位素分异,湿的安山岩可以通过这种方式演变成花岗质成分,因此这个过程可能对陆壳的产生和演化有重大影响。如果温度梯度在岩浆作用中能长期存在,热扩散就可以产生稳定同位素的分馏,这一机制有别于传统的平衡和动力学同位素分馏。 而多个稳定同位素体系的正相关关系是示踪热迁移过程的最有力证据。在热扩散过程中,流体承载的物质的浓度和它的索瑞系数有关。但是这个系数对体系的很多参数非常敏感,变化极大,因此对热扩散效应的研究产生极大的困难。对热扩散实验的镁、钙和铁同位素测量表明,同位素比值的变化与体系的化学组成以及总温度无关,只和温度变化的幅度有关,这意味着即使元素的索瑞系数变化多端,某一元素的同位素之间的索瑞系数的差别总为常数。这一发现有助于简化对热扩散和索瑞系数这一基础物理问题的研究 。  相似文献   

11.
《Geochimica et cosmochimica acta》1999,63(11-12):1781-1786
Oxygen isotope exchange between calcite and forsterite were investigated in the presence of a large amount of supercritical fluid. The experiments were conducted in standard cold-seal pressure vessels at 680°C and 500 MPa in the T-P-XCO2 stability field of the calcite-forsterite assemblage for 2, 5, 10, 20, 40 and 80 days, respectively. The weight ratio of mineral to fluid in the starting mixture is 1.46; the fluid was a mixture of H2O and CO2 with the mole fraction of CO2 being 0.1. The results show that the oxygen isotope exchange between the minerals was accomplished via mineral-fluid exchange by a dual-mechanism, i.e. initial rapid exchange due to Ostwald ripening of both calcite and forsterite, followed by a slower diffusion-controlled process. Furthermore, for the given fluid composition, calcite shows a greater rate of dissolution-recrystallization and oxygen isotope exchange with fluid than forsterite. As a result, oxygen isotope fractionations between calcite and forsterite and between the minerals and the fluid can simply pass the equilibrium fractionations with time and even lead to crossover behavior. Once diffusion becomes a primary mechanism for further isotope exchange in the three-phase system, the rate of oxygen diffusion in calcite is equal to, or slightly less than that in forsterite.  相似文献   

12.
Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO2+H2O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove  相似文献   

13.
To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO3)2 solution at 0 to 50°C in the presence of Mg2+ or SO42−. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO2 gas in the initial Ca(HCO3)2 solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO3 minerals slowly precipitated by the CaCO3 or NaHCO3 dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO2 gas in the initial Ca(HCO3)2 solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO2 gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:
  相似文献   

14.
The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al2O3), goethite (α-FeOOH), quartz (α-SiO2), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)sorb-Fe(II)aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ56/54Fe(II)aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)aq to be affected by sorption.  相似文献   

15.
The assumption of oxygen isotope and major element equilibrium during prograde metamorphism was tested using staurolite‐grade pelitic schists that have undergone sequential porphyroblast growth and multiple episodes of recrystallization of matrix minerals and foliation development. Textural relationships are used to infer a metamorphic history that involves garnet growth followed by staurolite growth, with each porphyroblast growth event followed by at least one period of recrystallization of matrix minerals. Conventional geothermobarometry using Qtz–Grt–Pl–Ms–Bt ± St equilibria yields peak P–T conditions of c. 625 °C at 9–11 kbar, consistent with KMnFMASH petrogenetic grid predictions for stability of the assemblage Grt + St + Bt. Qtz–Grt oxygen isotope fractionations yield apparent temperatures of c. 590 °C and Qtz–St fractionations yield an apparent temperature of c. 595 °C. Diffusional modelling indicates that quartz isotopic compositions were reset by c. 30 °C via retrograde isotopic diffusional exchange with micas. The isotopic temperatures appear to be in excellent agreement with one another, and suggest oxygen isotope equilibrium was attained between garnet and staurolite at c. 625 °C. However, the agreement of Qtz–Grt and Qtz–Str isotopic temperatures is not consistent with petrographic observations (garnet grew before staurolite) and petrogenetic grid constraints that predict that garnet grows over a temperature interval of c. 525–550 °C. Given that: (i) oxygen diffusion rates in staurolite and garnet are slow enough to render an individual porphyroblast effectively closed to exchange after it forms; and (ii) matrix minerals are able to exchange isotopes via recrystallization during each period of deformation; garnet and staurolite could not have simultaneously achieved oxygen isotope equilibrium with each other or with minerals in the recrystallized matrix. Thus, the Qtz–Grt fractionations, which yield apparent temperatures that are in apparent agreement with peak metamorphic temperature and apparent temperatures for Qtz–St fractionations, cannot be fractionations resulting from equilibrium isotopic exchange. Instead, they are apparent fractionations between porphyroblasts formed at different temperature and times in the prograde P–T–D path, and quartz that recrystallized and exchanged with micas and plagioclase during several phases of deformation.  相似文献   

16.
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   

17.
Over the last decade it has become apparent that Li isotopes may be a good proxy to trace silicate weathering. However, the exact mechanisms which drive the behaviour of Li isotopes in surface environments are not totally understood and there is a need to better calibrate and characterize this proxy. In this study, we analysed the Li concentrations and isotopic compositions in the various surface reservoirs (soils, rocks, waters and plants) of a small forested granitic catchment located in the Vosges Mountains (Strengbach catchment, France, OHGE http://ohge.u-strasbg.fr). Li fluxes were calculated in both soil profiles and at the basin scale and it was found that even in this forested basin, atmospheric inputs and litter fall represented a minor flux compared to input derived from the weathering of rocks and soil minerals (which together represent a minimum of 70% of dissolved Li). Li isotope ratios in soil pore waters show large depth dependent variations. Average dissolved δ7Li decreases from −1.1‰ to −14.4‰ between 0 and −30 cm, but is +30.7‰ at −60 cm. This range of Li isotopic compositions is very large and it encompasses almost the entire range of terrestrial Li isotope compositions that have been previously reported. We interpret these variations to result from both the dissolution and precipitation of secondary phases. Large isotopic variations were also measured in the springs and stream waters, with δ7Li varying from +5.3‰ to +19.6‰. δ7Li increases from the top to the bottom of the basin and also covaries with discharge at the outlet. These variations are interpreted to reflect isotopic fractionations occurring during secondary phase precipitation along the water pathway through the rocks. We suggest that the dissolved δ7Li increases with increasing residence time of waters through the rocks, and so with increasing time of interaction between waters and solids. A dissolution precipitation model was used to fit the dissolved Li isotopic compositions. It was found that the isotopic compositions of springs and stream waters are explicable by an isotopic fractionation of −5‰ to −14‰ (best fit −10.8‰), in agreement with Li incorporation into clay. In soil solutions, it was found that isotopic fractionation during secondary precipitation is larger (at least −23‰), suggesting a major role for different secondary phases, such as iron oxides that maybe incorporate Li with a higher isotope fractionation.  相似文献   

18.
Li isotope fractionation in peridotites and mafic melts   总被引：4，自引：0，他引：4  
We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of 7Li/6Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ7Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ7Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ7Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ7Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ7Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ7Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.  相似文献   

19.
We report results of experiments constraining oxygen isotope fractionations between CO2 vapor and Na-rich melilitic melt at 1 bar and 1250 and 1400°C. The fractionation factor constrained by bracketed experiments, 1000.lnαCO2-Na melilitic melt, is 2.65±0.25 ‰ (±2σ; n=92) at 1250°C and 2.16±0.16 ‰ (2σ; n=16) at 1400°C. These values are independent of Na content over the range investigated (7.5 to 13.0 wt. % Na2O). We combine these data with the known reduced partition function ratio of CO2 to obtain an equation describing the reduced partition function ratio of Na-rich melilite melt as a function of temperature. We also fit previously measured CO2-melt or -glass fractionations to obtain temperature-dependent reduced partition function ratios for all experimentally studied melts and glasses (including silica, rhyolite, albite, anorthite, Na-rich melilite, and basalt). The systematics of these data suggest that reduced partition function ratios of silicate melts can be approximated either by using the Garlick index (a measure of the polymerization of the melt) or by describing melts as mixtures of normative minerals or equivalent melt compositions. These systematics suggest oxygen isotope fractionation between basalt and olivine at 1300°C of approximately 0.4 to 0.5‰, consistent with most (but not all) basalt glass-olivine fractionations measured in terrestrial and lunar basalts.  相似文献   

20.
The pilot hole of the Continental Deep Borehole (KTB) drilling project is located in the Bavarian Oberpfalz at the western margin of the Bohemian Massif. The 4-km deep borehole penetrated various paragneisses and minor orthogneisses with intercalations of amphibolites and metagabbros. The different lithologies have systematically different whole-rock oxygen isotope values and give little evidence for large scale water-rock interaction. Minor fluid interaction is well documented during retrograde metamorphism by non-equilibrium fractionations between refractory minerals (quartz, garnet and hornblende) and altered minerals (chlorite/biolite and feldspar). Ubiquitous vein mineralisation indicates fluid-induced retrogression at temperatures between 150°C and 400°C. The D values of hydroxylbearing minerals are very uniform in all lithologic units. The calculated hydrogen isotope composition of the fluid in equilibrium with matrix and vein minerals increases from -45 for metabasic rocks, to -20 for gneisses, to about -5 for vein minerals. The oxygen isotope composition of the fluid has been buffered by the rock and decreases with decreasing temperature because of increasing fractionations at low temperatures and low water-rock ratios. Modern fluids sampled from open cavities within the borehole have isotopic compositions that suggest a continuous fluid evolution during retrogression in a closed system. The 13C values of calcite and graphite also indicate closed system mixing processes.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号