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1.
郑永飞  李一良 《地学前缘》1998,5(2):261-274
应用理论计算、实验测定和经验估计三种方法均能获取含固体矿物体系的氧同位素分馏系数,其中高温高压实验研究不仅能够得到物相之间的同位素平衡分馏系数,而且能够提供与同位素交换动力学和机理有关的信息。同位素分馏系数的实验校准方法已经由原来的两相体系(矿物H2O、矿物CO2和矿物CaCO3)交换发展为三相体系(CaCO3矿物流体)交换,化学合成、重结晶和矿物反应技术得到了进一步应用。本文评述了近十年来这一领域的研究进展,着重介绍了H2O、CO2和CaCO3作为交换介质进行氧同位素分馏系数校准的技术原理和结果,探讨了热液和碳酸盐交换实验结果不一致的原因。  相似文献   

2.
郑永飞  赵子福 《岩石学报》2011,27(2):345-364
在特定的地质事件过程中,矿物等时线放射体系是否达到并且保持了平衡是变质岩Sm-Nd和Rb-Sr同位素年代学中的一个重要问题。在这个问题上矿物对O同位素测温与矿物等时线定年相似,因此两者之间可以相互制约。在岩浆岩和变质岩中,矿物中Sm-Nd、Sr和O之间的扩散速率在无水的条件下一般具有可比性,因此矿物之间O同位素的平衡状态可以用来对Sm-Nd和Rb-Sr定年的有效性进行检验。对大别-苏鲁造山带超高压变质岩的Sm-Nd和Rb-Sr等时线矿物进行O同位素测温,得到Sm-Nd等时线有时给出三叠纪年龄,有时给出非三叠纪年龄;对应的矿物O同位素分馏分别处于平衡和不平衡状态。对于引起非三叠纪等时线年龄的原因,一方面可以是由于榴辉岩相变质过程中同位素体系没有达到平衡,另一方面则可能角闪岩相退变质作用打破了平衡。等时线矿物中初始同位素比值的均一化速率主要受慢扩散矿物的影响,而矿物等时线时钟的启动主要受高母/子比值矿物控制。因此在变质作用过程中,只有当高母/子比值矿物同时具有快的放射成因同位素扩散速率,才可能得到有效的矿物等时线来用于变质年龄的测定。根据不同矿物中不同元素在扩散速率上的差异,能够定量估计大陆碰撞过程中榴辉岩相变质的持续时间。应用增量方法和离子孔隙度经验模型,不仅分别能够从理论上准确计算所有固体矿物的氧同位素分馏系数和获得不同矿物中元素的扩散参数,而且分别能够定量预测热力学平衡条件下共生矿物之间的18O富集顺序和相同条件下矿物中元素扩散速率的相对快慢。  相似文献   

3.
胶南榴辉岩矿物氧同位素平衡及其Sm-Nd年代学制约   总被引:2,自引:4,他引:2  
对苏鲁地体中的胶南榴辉岩进行了矿物氧同位素分析,并与同一手标本矿物的Sm-Nd内部等时线定年和Nd-Sr同位素分布进行了对比。研究表明,石榴子石与绿辉石之间的氧同位素平衡与否能够对矿物Sm-Nd同位素体系的平衡状况和内部等时线定年结果的有效性给予直接制约。合理的石榴子石+绿辉石Sm-Nd内部等时线年龄产于两矿物之间达到并在峰变质条件下保持氧同位素平衡的样品中,而两矿物之间处于氧同位素不平衡的样品不能给出正确的Sm-Nd内部等时线年龄。同一矿物在手标本尺度出现显著的O-Nd-Sr同位素不均一性,据此对这些元素在石榴子石和绿辉石中的扩散速率顺序进行了估计,不仅得到了与实验扩散系数相吻合的结果,而且由此估计出在峰变质条件下达到矿物内部同位素均一化所需要的时间应大于10Ma。  相似文献   

4.
郑永飞 《地球学报》1997,18(Z1):248-250
应用增量方法不仅能够从理论上准确计算所有固体矿物的O同位素分馏系数,而且能够定量预测;(1)热力学平衡条件下共生矿物之间的18O富集顺序;(2)岩石化学成分与O同位素组成之间的关系;(3)矿物结构变化对O同位素组成的影响;(4)同质多相转变和矿物反应中的氧同位素继承性。本文对这些规律性预测进行了概要性介绍,并给出实例予以说明。  相似文献   

5.
矿床地球化学应用   总被引:37,自引:13,他引:37  
郑永飞 《矿床地质》2001,20(1):57-70,85
稳定同位素方法已成为现代地球科学研究的重要手段之一,稳定同位素体系的理论模式及其地球化学应用是国际上地球化学研究的前沿方向之一。本文概括了热液体系内成矿地球化学过程引起稳定同位素组成变化的定量理论模式,包括热液矿物之间的同位素平衡的判断、热液去气和矿物沉淀的储库效应、二元混合与矿床成因等。这些模型对于确定成矿温度、鉴定成矿流体源区和推测成矿地球化学机理提供了更为合理的同位素数据定量解释基础。  相似文献   

6.
地质流体中不同络合物之间的稳定同位素平衡分馏系数是利用稳定同位素示踪地质流体演化过程的必要前提.但由于受实验条件的限制,流体中部分元素不同络合物之间的同位素分馏系数难以通过实验精确测定.基于第一性原理的理论计算是获得溶液中不同络合物之间稳定同位素平衡分馏系数的一种重要手段,能够获取各种极端条件下同位素分馏系数.在应用第...  相似文献   

7.
稳定同位素平衡分馏资料已广泛应用于地质研究中,对探讨成矿物质、成矿流体来源、矿床成因及成矿机理等起了重要作用。然而其应用的前提必须假设:(1)地质体系中共生矿物间及与介质流体间已达到同位素平衡;(2)矿物的形成温度作为终止同位素交换的封闭温度。但大量的资料表明,许多地质体中共生矿物间并非都达到了同位素平衡,矿物的形成温度并非就是同位素交换的封闭温度,这正是目前一些同位素资料互相矛盾,不能得到合理介释的原因所在。例如,同位素地温计与相平衡证据不符,共生矿物之间没有统一的同位素平衡关系,由共生矿物对计算的同位素温度不一致;同一矿物或共生矿物的氧、氧同位素组成之间及硫酸盐矿物中硫、氧同位素组成之间的不一致等等。这些都反映出仅用平衡分馏原理不能全面、合理地解释地质问题。地质过程是一个漫长而复杂的演化发展过程,许多矿  相似文献   

8.
以工作程度最高的造山型金矿为例,通过对国内外大量实例的剖析、讨论和综合,认为热液矿床稳定同位素组成不仅受成矿流体源区的制约,还不同程度地依赖于成矿热液复杂的演化历程,包括流体在运移过程中与围岩的同位素交换、沉淀过程中的同位素分馏以及后期可能的改造等多种因素。硫同位素很易因水岩反应、相分离、氧化作用、多种流体混合等过程而发生同位素分馏,从而使同一矿床不同产状矿脉,甚至同一期黄铁矿的S同位素出现显著差异。碳同位素测试常用的碳酸盐矿物大多是成矿晚期热液矿物,特别是方解石,其经历了水岩反应、CH4和CO2不混溶的相分离和流体的长期演化,往往指向复杂的多来源特征。氢氧同位素易因水岩反应而偏离源区特征,也易受后期改造而显示出大气水混入等特征。金矿中含氮矿物中氮含量和氮同位素值大致与变质岩和花岗岩值范围重合,这方面的研究还需进一步完善。因此,不能简单根据测定结果直接投图判断成矿流体的可能来源,而需要综合多种方法并结合矿区地质实际情况剔除成矿过程对稳定同位素的影响后才能更好地约束造山型金矿成矿流体来源。深入研究同位素沿着流体通道的空间变化和各成矿阶段的时间演化或许不仅能够查明成矿流体的来源,而且能够揭示流体的演化轨迹和成矿过程。  相似文献   

9.
硅酸盐和金属氧化物矿物氧同位素组成的CO2激光氟化分析   总被引:9,自引:0,他引:9  
我室采用MIR-10型CO2激光器,在一种富BrF5的氛围中使激光对硅酸盐和氧化物矿物样品加热形成O2,经多次纯化后用5A的分子筛吸收,再直接送至气体质谱仪进行氧同位素比值测定.这个实验流程与传统方法相比的改进不仅在使用激光加热技术及样品的放置上,而且在直接采用O2而不是CO2进行质谱测定.采用O2进行直接分析的优点不仅避免了向CO2转化过程中的潜在同位素分馏,而且能够得到样品的δ17O值,因此为宇宙样品分析提供了可能.CO2激光氟化技术的优点是所需样品量小(可低达1~2 mg),因此能够分析微小岩石区域或单矿物晶体内的氧同位素分布.同时,激光可以达到非常高的温度(>4000K),因此能够对某些难熔矿物(如锆石、蓝晶石、橄榄石等)进行氧同位素分析.  相似文献   

10.
桂林洞穴沉积物的氧、碳同位素特征   总被引:7,自引:1,他引:7  
汪训一 《中国岩溶》1985,(Z1):149-154
<正>在现代稳定同位素研究中,往往利用达到同位素平衡的一对共生矿物或矿物——水之间的同位素组成来作为地质温度计,以了解其形成时的温度。对于岩溶洞穴环境来说,主要是利用方解石——水之间的同位素平衡反应。C.H.Hendy(1971))详细研究了洞穴堆积过程中可能出现的各种地球化学作用及其对同位素分布的影响,认为当CO2从水中迅速逸失或进行水的蒸发作用时,产生同位素动力分馏,沉积物中相对富集的O18,不能作为古温度标志,而只有当CO2从水中缓慢逸出时,方解石和水之间氧同位素的平衡反应方可作为地质温度计。其平衡常数(K)主要取决于形成的温度。  相似文献   

11.
Stable isotope fractionations between minerals are functions of the fundamental vibrational frequencies of the minerals and therefore bear on several topics of mineralogical interest. Isotopic compositions of the elements H, C, O, Si, and S can now be determined routinely in almost any mineral. A summary has been made of both published and new results of laboratory investigations, analyses of natural materials, and theoretical considerations which bear on the importance of temperature, pressure, chemical composition and crystal structure to the isotopic properties of minerals. It is shown that stable isotope studies can sometimes provide evidence for elucidating details of crystal structure and can be a powerful tool for use in tracing the reaction paths of mineralogical reactions.  相似文献   

12.
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   

13.
The influence of NaCl, CaCl2, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl2 on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl2 has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.  相似文献   

14.
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   

15.
This article summarizes some recent results obtained on the physical properties of environmental minerals, mostly kaolinite-group minerals and Fe- and Al-(hydr)oxides occurring in lateritic soils. The defective structure of these minerals, including impurities, stacking faults and radiation-induced defects, is probed using infrared spectroscopy and electron paramagnetic resonance. Resulting information bears on models of soil formation and transformation mechanisms of minerals in low-temperature environments. We underline the increasing impact of quantum chemical modeling in this field, providing straightforward interpretations of spectroscopic signals and overcoming the limits of fingerprint approaches. Importantly, the first-principles modeling of isotopic fractionation factors provides new links between mineralogical and geochemical investigations of secondary minerals.  相似文献   

16.
Iron isotope and major- and minor-element compositions of coexisting olivine, clinopyroxene, and orthopyroxene from eight spinel peridotite mantle xenoliths; olivine, magnetite, amphibole, and biotite from four andesitic volcanic rocks; and garnet and clinopyroxene from seven garnet peridotite and eclogites have been measured to evaluate if inter-mineral Fe isotope fractionation occurs in high-temperature igneous and metamorphic minerals and if isotopic fractionation is related to equilibrium Fe isotope partitioning or a result of open-system behavior. There is no measurable fractionation between silicate minerals and magnetite in andesitic volcanic rocks, nor between olivine and orthopyroxene in spinel peridotite mantle xenoliths. There are some inter-mineral differences (up to 0.2 in 56Fe/54Fe) in the Fe isotope composition of coexisting olivine and clinopyroxene in spinel peridotites. The Fe isotope fractionation observed between clinopyroxene and olivine appears to be a result of open-system behavior based on a positive correlation between the Δ56Feclinopyroxene-olivine fractionation and the δ56Fe value of clinopyroxene and olivine. There is also a significant difference in the isotopic compositions of garnet and clinopyroxene in garnet peridotites and eclogites, where the average Δ56Feclinopyroxene-garnet fractionation is +0.32 ± 0.07 for six of the seven samples. The one sample that has a lower Δ56Feclinopyroxene-garnet fractionation of 0.08 has a low Ca content in garnet, which may reflect some crystal chemical control on Fe isotope fractionation. The Fe isotope variability in mantle-derived minerals is interpreted to reflect subduction of isotopically variable oceanic crust, followed by transport through metasomatic fluids. Isotopic variability in the mantle might also occur during crystal fractionation of basaltic magmas within the mantle if garnet is a liquidus phase. The isotopic variations in the mantle are apparently homogenized during melting processes, producing homogenous Fe isotope compositions during crust formation.  相似文献   

17.
王相力  卫炜 《地学前缘》2020,27(3):78-103
随着多接收质谱仪分析技术的进步,铬稳定同位素体系在最近二十几年的环境科学和地球化学中得到了越来越广泛的应用。铬元素属于氧化还原敏感元素,在氧化还原反应过程中伴随着较大的同位素分馏。因此,铬同位素在指示现代或古代环境的氧化还原状态方面有着重要的应用。同时,铬也是中度相容和轻度亲铁元素,使得铬稳定同位素体系也可用来制约高温地质过程(如核幔分异、地幔熔融和岩浆分异结晶等)以及地外行星的演化。本综述首先介绍铬稳定同位素体系,随后讲述分析方法、铬同位素分馏原理以及铬同位素在高温、低温地球化学中的应用。  相似文献   

18.
Calculation of sulfur isotope fractionation in sulfides   总被引:3,自引:0,他引:3  
The increment method has been successfully applied to calculate thermodynamic isotope fractionation factors of oxygen in silicates, oxides, carbonates, and sulfates. In this paper, we modified the increment method to calculate thermodynamic isotope fractionation factors of sulfur in sulfides, based on chemical features of sulfur-metal bonds and crystal features of sulfide minerals. To approximate the bond strength of sulfides, a new constant, known as the Madelung constant, was introduced. The increment method was then extended to calculate the reduced partition function ratios of sphalerite, chalcopyrite, galena, pyrrhotite, greenockite, bornite, cubanite, sulvanite, and violarite, as well as the isotope fractionation factors between them over the temperature range from 0 to 1000 °C. The order of 34S enrichment in these nine minerals is pyrrhotite > greenockite > sphalerite > chalcopyrite > cubanite > sulvanite > bornite > violarite > galena. Our improved method constitutes another model for calculating the thermodynamic isotope fractionation factors of sulfur in sulfides of geochemical interest.  相似文献   

19.
Clay minerals record chemical data about the past, acting like natural computer memory chips. To retrieve the data we must understand how they are stored. To achieve this we have examined the isotopic information revealed by two trace elements, lithium and boron, that are incorporated into the common clay minerals illite-smectite (I-S) during diagenesis. We used hydrothermal experiments at 300°C, 100 MPa, to speed up the reaction of smectite to illite that normally occurs during slow (10-100 Ma) sediment burial. During illitization, Li substitutes into the octahedral sites and B enters the tetrahedral sites of the silicate framework. Both Li and B are also adsorbed in the interlayer of smectite, but Li is preferred over B in the exchange sites. To determine the equilibrium isotope fractionation of the two trace elements it is important to remove these adsorbed interlayer species. By measuring the isotopic composition of Li and B in the silicate framework during reaction, we can address the relative timing of element exchange in the different crystallographic sites. Furthermore, because illitization of smectite is a crystal growth process (not an isomorphous replacement) we have examined the effect of crystal size on the isotope fractionation.The results show that Li and B approach an isotopic steady state when R1 ordering occurs, long before oxygen isotopes equilibrate with the fluid. The isotopic fractionation (αmineral-water) for Li (0.989) is similar to that for B (0.984) at 300°C. However, when separated into <0.2, 0.2-2.0, and >2.0 μm fractions, there are significant differences in measured isotope ratios by as much as 9‰. Crystal growth mechanisms and surface energy effects of nanoscale crystals may explain the observed isotopic differences. The fact that different crystals equilibrate at different rates (based on size) may be applied to natural samples to reveal the changing paleofluid history, provided we understand the conditions of equilibrium. This has very important implications for the interpretation of diagenetic environments, fluid flow, and surficial geochemical cycling.  相似文献   

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