水─岩交换体系氢同位素动力分馏

水─岩交换体系氢同位素动力分馏张理刚，陈振胜，刘敬秀，于桂香（地质矿产部宜昌地质矿产研究所，宜昌４４３００３）关键词氢同位素、动力分馏、水—岩交换体系以往对成矿流体中δＤ值的研究，一般采用测定矿物包裹体水的δＤ值；也有测定含羟基矿物的δＤ值，结合温度...     

电气石和水之间的氢同位素分馏

作者对电气-水体系氢同位素平衡分馏和动力学分馏和动力学分馏开展了实验研究，丰富了羟基矿物氢同位素分馏资料。本文对该研究的实验技术、分析方法作了介绍，并对实验结果进行讨论与国外已有的该方面的资料作了对比。在800-650℃时电气石和水之间氢同位素平衡分馏系数与温度间线性关系为103lna电气石-水=-28.24（106/T2）+2.60；交换速率常数与温度间关系为lnk2=-0.19-6.70（103/T）     

物相之间氧同位素分馏的高温高压实验研究

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。     

碳酸钙-水体系氧同位素分馏系数的低温实验研究

碳酸钙是古气候和沉积岩稳定同位素地球化学研究中最常用的矿物 ,因此对碳酸钙水体系氧同位素分馏系数的实验校准已成为稳定同位素地球化学诞生以来的热点和前沿课题。但由于碳酸钙在自然界存在 3种同质多象变体 (方解石、文石和六方方解石 ) ,使人们对碳酸钙矿物与水之间氧同位素分馏系数的实验测定结果存在较大差别 ,当应用到同位素地质测温时 ,会给出显著不同的温度值。正确选用合理的方解石水或文石水体系分馏曲线 ,对低温和环境地球化学研究和应用具有重要价值。文章系统总结和评述了碳酸钙水体系氧同位素分馏系数实验校准的历史、方法和结果 ,对前人在表达方式上的不一致进行了统一 ,对氧同位素分馏的盐效应、动力氧同位素分馏效应和同质多象转变过程中的氧同位素继承性进行了讨论。通过对前人大量实验数据的系统处理并与理论计算相比较 ,推荐了热力学上平衡的方解石水体系氧同位素分馏方程 ,而对于文石水体系 ,理论计算结果尚有待于实验证实。     

中酸性硅酸盐熔体-水体系氢同位素分馏的压力效应

对0．2－2000MPa条件下钠长石熔体，钾长石熔体以及0．2－150MPa条件下流纹岩熔体－－水体系的氢同位素分馏实验数据进行了筹压拟合，发现硅酸盐熔体与水之间的氢同位素分馏存在显著的压力效应，在800，1000和1200度条件下对钠长石熔体，水体系和流夺熔体－－水体系氢同位素分馏压力方程进行的等温拟合表明，只有在特定的压力条件下才可以用钠长石熔体－水体系来近似流纹岩熔体－－水体系的氢同位素分馏行为，当压力超过临界值时，硅酸盐熔体－水体系氢同位素分馏会发生变化，本文拟合的硅酸盐熔体－水体系氢同位素分馏等值线在P－T空间的形态变化特征与矿物－水体系存在较大差异，依据流纹岩熔体与水之间氢同位素分馏的压力效应，成功地模拟了美国西部Glass Creek流纹岩δD值和水含量变化规律与岩浆去气之间的关系。     

二氧化钛—水体系氧同位素分馏系数的实验研究

对ＴｉＯ２的两种常见同质多像变体金红石和锐钛矿与水之间的氧同位素分馏系数的实验研究进行了系统的总结和评述。水热晶化法和水热氧化法以及低温水解法获得的实验金红石－水体系分馏系数与增量方法理论计算结果相一致。低温水解法获得的够太矿－水体系分馏可能是一种不平衡分馏,其分馏系数的大小决定于锐钛矿的形成机制。同时,低温水解实验还揭示,在低温矿物形成和同质多像转变过程中可能存在氧同位素继承性,这对解释低温环境     

水镁石—水体系氧同位素分馏系数的低温实验研究

在15—120℃的低温范围内分别应用氮化镁法、氯化镁法和氧化镁法3种化学合成方法,对水镁石-水体系氧同位素分馏系数进行了实验测定。所有合成样品的晶体结构均由XRD测定,其形貌特征则由SEM确定。应用3种不同合成方法得到了一致的水镁石—水体系氧同位素分馏系数,证明同位素平衡分馏已经达到。在实验温度范围内,水镁石—水体系氧同位素分馏系数主要决定于温度,而溶液的酸碱度、化学组分和陈化时间的影响不明显。由实验数据得到的氧同位素分馏曲线方程为:10~3Inα=1.59×10~6/T~2-14.10(r=0.9921)。结合前人对三水铝石—水体系和针铁矿—水体系氧同位素分馏系数的低温实验测定,可以得到氢氧化物中金属M—OH键的~(18)O富集顺序:Al~(3+)-OH>Fe~(3+)-OH>Mg~(2+)-OH。应用化学合成方法实验测定低温条件下水镁石—水体系氧同位素分馏系数,不仅克服了同位素交换反应实验的一些缺陷(如交换速率缓慢、仪器设备复杂昂贵等),而且可以应用不同的化学合成反应机理来检验同位素平衡是否达到,这为研究低温地球化学过程作用提供了有价值的基本参数。     

文石-水体系氧同位素分馏系数的低温实验研究

采用缓慢分解法和“两步法”的附晶生长法,在低温(0℃～70℃)下实验合成纯文石型碳酸 钙矿物,以XRD和SEM技术对合成矿物的相组成和形貌进行了鉴定。将XRD与SEM及氧同位素分 析技术相结合,研究了文石的生成速率与氧同位素分馏之间关系。对0℃、25℃和50℃条件 下采用缓慢分解法合成的文石进行SEM观察发现,随着温度升高,矿物生成速率加快,氧同 位素分馏逐渐趋于不平衡,导致50℃条件下获得的文石-水体系氧同位素分馏是一种不平衡 分馏,而0℃和25℃条件下获得的低值代表平衡分馏。将0℃和25℃以下采用缓慢分解法获得 的文石-水体系分馏低值与采用“两步法”的附晶生长法在50℃和70℃条件下获得的文石- 水体系平衡分馏数据相结合,得到0℃～70℃范围内文石-水体系氧同位素平衡分馏方程为 ：103lnα=20.41×103T－41.42。这个实验结果不仅与增量方法理论计算结 果一致,而且与前人低温实验获得的文石或文石与方解石混合相碳酸钙-水体系,以及生物 成因文石-水体系的氧同位素分馏结果相近。这是首次根据实验确定的无机成因文石-水体 系热力学平衡氧同位素分馏系数,因此对于无机成因文石在古沉积环境和古气候研究中的应 用具有重要参考价值。     

非氢键羟基矿物H同位素平衡分馏议程通式

本文对H同位素平衡分馏系数（αe）与温度（T）、矿物化学组成（M）、羟基振动频率（f）之间的关系作了详细研究，并得出非氢键羟基矿物在450-850℃温度范围内，H同位素平衡分馏方程通式。     

碳酸钙-水体系氧同位素平衡及稳态分馏的低温实验研究

采用“一步”和“两步”的直接沉淀法和附晶生长法在 5 0℃和 70℃分别合成碳钡矿和文石 ,测定不同条件下合成矿物与水之间的氧同位素分馏 ,结果显示 ,文石—水体系氧同位素分馏机理分两步 :(1) [CO3 ]2 - 与H2 O的氧同位素交换和平衡 ,此过程是文石 水氧同位素平衡的决速率步骤 ;(2 )与H2 O平衡以后的 [CO3 ]2 - 与Ca2 +]结合生成文石 ,此过程体现矿物形成过程中氧同位素分馏的结构效应。在此基础上 ,采用缓慢沉淀法和“两步”的附晶生长法获得了 0～ 70℃的文石 水体系氧同位素平衡分馏方程。采用“一步”和“两步”的附晶生长法在 5 0℃和 70℃合成文石 ,文石在溶液中经同质多象转变成次生方解石 ;结合文献数据 ,获得 0～ 70℃范围内的方解石 水体系稳态氧同位素分馏方程。     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

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.     

矿物稳定同位素地球化学研究

通过测定矿物中元素H ,C ,O和S的同位素比值 ,认识矿物体系中的同位素效应 ,不仅能够确定矿物之间和矿物与流体之间的同位素平衡关系 ,而且能够了解影响矿物平衡和动力学同位素性质的因素。文中评述了稳定同位素分馏系数校准的理论计算、实验测定和经验估计方法 ,讨论温度、压力、化学成分和晶体结构等对矿物同位素性质的影响。由于同位素效应取决于矿物的物理和化学性质 ,因此应用稳定同位素来作为示踪剂不仅能够追索各种矿物学反应的路径 ,而且能够提供证据来阐明矿物晶体结构的某些细节。     

Experimental hydrogen isotope studies III: Diffusion of hydrogen in hydrous minerals,and stable isotope exchange in metamorphic rocks

Diffusion parameters for hydrogen diffusion in epidote-group minerals and micas have been measured under hydrothermal conditions, or calculated from existing experimental data, for bulk hydrogen isotope exchange experiments between hydrous minerals and water. Activation energies in the range 14 to 31 kcals/g-atom H are comparable to those derived by application of kinetic theory to experimental hydrogen isotope exchange data, and to those for oxygen diffusion in minerals under hydrothermal conditions. Diffusion of hydrogen in epidote is about four orders of magnitude faster than in muscovite, and about two orders of magnitude faster than in zoisite. Hydrogen diffusion in micas is about five orders of magnitude faster than oxygen diffusion, and hydrogen transport occurs dominantly parallel to the layers rather than parallel to the c-axis as for oxygen.Rapid hydrogen transport in minerals may proceed by hydrolysis of Si-O and Al-O bonds, followed by exchange of hydrolyzed oxygens with slower-diffusing (OH) or H₂O. Water appears to be essential for stable isotope exchange between minerals in slowly cooling metamorphic rocks.Stable isotope data for regional metamorphic mineral assemblages suggests that water is usually present in small amounts during cooling of prograde regional metamorphic systems, and estimated closure temperatures for cessation of stable isotope exchange are often more comparable to those calculated from diffusion data than to likely temperatures of metamorphism.Alpine deformation of the Hercynian Monte Rose Granite (Frey et al. 1976) permitted access of water and initiated stable isotope exchange amongst coexisting minerals. The diffusional behaviour of species in relict Hercynian muscovites is consistent with available experimental diffusion data.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

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.     

磷酸盐氧同位素组成的测定方法及分馏机理研究进展

磷酸盐氧同位素组成在古气候和磷的生物地球化学循环研究中都具有十分重要的意义.测定方法和同位素的分馏机理是该类研究的基础.国际上已开展了一系列磷酸盐氧同位素的测定方法和分馏机理研究.在测定方法上,由初期的间接法,经高温还原/裂解法到氟化法,再演化到改进后的高温还原法(包括TC/EA-IRMS法),甚至激光原位技术,样品由实验室纯化学试剂扩展到各种复杂地质样品,在测量精确度、测量速度、样品用量、安全性和技术要求方面都有巨大改进.在分馏机理上,①尽管Longinelli等建立的关系式已获得了天然样品的验证,并认为是平衡分馏,但实验室模拟结果与其还存在较大差异(即没有达到平衡分馏).②在地表温度和pH条件下,无机过程均不会造成水体中溶解态磷酸盐和水之间的氧同位素交换.在高温(>70℃)及不同pH条件下,即使没有生物作用也会造成溶解磷酸盐和水分子之间进行氧的同位素交换,但不同实验室之间结果不一致.③在生物作用存在下,溶解无机磷酸盐和水之间在地表环境会发生强烈氧同位素交换,但除了PPase外,其余均没有达到平衡值.④磷灰石的氧同位素组成要比形成它的溶解态磷酸盐的值高1‰～1.4‰,因此在把Longinelli等关系式用于溶解态磷酸盐和水体系时,需要考虑该因素.同位素平衡分馏和条件有关,认为无机条件下的高温(>70℃)实验结果不一致,以及有生物参与的培养实验结果偏离平衡值,都是实验条件不同所致,包括pH、磷酸盐浓度、生物种类、生物量等.     

碳酸盐矿物氧同位素分馏的理论研究

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。     

高温下非传统稳定同位素分馏

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 。     

Mineral oxygen isotope and hydroxyl content changes in ultrahigh-pressure eclogite–gneiss contacts from Chinese Continental Scientific Drilling Project cores

A combined study of mineral O isotopes and hydroxyl contents was carried out for the contacts between ultrahigh‐pressure eclogite and gneiss from main hole of the Chinese Continental Scientific Drilling Project in the Sulu orogen. While there is a large δ¹⁸O variation from ?8.3 to 7.3‰ for all minerals, different styles of mineral‐pair fractionation occur at the boundaries of different lithologies. Both equilibrium and disequilibrium O isotope fractionations are observed between quartz and the other minerals, with reversed fractionations between omphacite and garnet in some samples of eclogite. This suggests that both eclogite and gneiss acquired their negative δ¹⁸O values by meteoric‐hydrothermal alteration of their protoliths at high temperatures before subduction, and that fluid‐assisted O isotope exchange did take place across the boundary of different lithologies at local scales during amphibolite‐facies retrogression. Fourier Transform Infrared Spectroscopy analysis yielded H₂O concentrations of 50 to 1144 p.p.m. (by weight) for garnet and 139 to 751 p.p.m. for omphacite. The state of equilibrium or disequilibrium O isotope fractionations between omphacite and garnet are correlated with variations in their water content at local scales, indicating that the internally derived fluid plays a critical role in retrograde metamorphism during exhumation. The retrograde metamorphism results in mineral reactions and O isotope disequilibria between some of the minerals, but the fluid for retrogression was derived from the decompression exsolution of structural hydroxyl and thus internally buffered in the O isotope composition. A quantitative estimate suggests that a hand specimen (3 × 6 × 9 cm) of eclogite composed of 70% garnet and 30% omphacite can release 0.316 g water by the decompression exsolution of structural hydroxyl, which can form 14.4 g amphibole during exhumation. This provides sufficient amounts of water for the amphibolite‐facies retrogression.