文石—水体系氧同位素分馏机理的实验研究

采用“附晶生长法”分别在５０和７０℃下合成文石下矿物,获得了两种不同的文石与水之间的氧同位素分馏关系。结果证明,文石与水之间氧同位素分馏的化学动力学机 为两步：（１）碳酸根与水之间进行氧同位素交换和平衡,即：「Ｃ＾１６Ｏ３」＾＾３－＋２Ｈ２＾１８Ｏ＝「Ｃ＾１８Ｏ３＾１６Ｏ」＾２－＋２Ｈ２Ｏ１６Ｏ;（２）与水平衡以后的「ＣＯ２」＾２－离子与Ｃａ＾２＋结合生成文石,即：Ｃａ＾２＋＋＿「Ｃ＾１８Ｏ２＾１     

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。     

白云母、高岭石矿物中羟基的o同位素分析方法研究

羟基矿物内部存在两种位于不同结构位置上的氧原子硅氧四面体氧和羟基氧,二者之间的Ｏ同位素分馏可能比任何共生矿物对都大,是一种潜在的单矿物同位素地质温度计。单矿物同位素地质温度计较矿物对同位素地质温度计有很多优点。准确测量矿物中羟基的Ｏ同位素组成是建立单矿物同位素地质温度计的关键。本文介绍了一种精确测量白云母、高岭石矿物中羟基的Ｏ同位素组成的新方法火焰加热真空脱水氟化法。δ１８ＯＯＨ的分析精度达到０３‰,羟基氧的提取率达到９９％～１００％。实验证明羟基矿物在高温真空脱水过程中不存在Ｏ同位素动力学分馏,羟基水     

矿物3CaO·3Al_2O_3·BaSO_4形成过程研究

ｅｏｒｅａｎｕ等［１］研究ＣａＯＡｌ２Ｏ３Ｍｘ（ＳＯ４）Ｙ［Ｍ＝Ｍｇ２＋、Ｓｒ２＋、Ｂａ２＋、Ｚｎ２＋、Ｆｅ２＋、Ｆｅ３＋、Ａｌ３］系统中,形成类似于矿物３ＣａＯ·３Ａｌ２Ｏ３·ＣａＳＯ４（硫铝酸钙）的可能性时,报道合成了新矿物３ＣａＯ·３Ａｌ２Ｏ３·ＢａＳＯ４（简写为３ＣＡ·ＢａＳＯ４）;部分学者［２,３］研究过它的胶凝性能等。在有关文献中,研究者制备研究用纯矿物的煅烧条件、获得样品的矿相组成不尽相同。如文献［１］在温度１４００℃保温２４０ｍｉｎ,制备的样品包括铝酸钙（ＣａＯ·Ａｌ２Ｏ３…     

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     

沉积CaCO3与金属离子界面反应动力学研究

金属离子与沉积碳酸盐之间２同反应动力学模拟实验表明,由于ＣａＣＯ３快速溶解和溶液ＰＨ急剧上升,大部分Ｐｂ＾２＋、Ｚｎ＾２＋离子与溶液中ＣＯ３＾２－和ＯＨ＾－离子反应生成白铅矿ＰｂＣＯ３、水白铅矿Ｐｂ３（ＯＨ）２（ＣＯ３）２,或Ｚｎ（ＯＨ）３和锌矿Ｚｎ（ＯＨ）６（ＣＯ３）２沉淀于体相溶液中,仅有少部分Ｐｂ＾２＋、Ｚｎ＾２＋通过扩散与ＣａＣＯ３表面发生离子交换反应。２５℃时,Ｐｂ＾２＋溶液中以白铅矿沉     

新书要览

新书要览同位素地球化学研究陈好寿主编，浙江大学出版社，１９９４，１６ｋ，３４０Ｐ系统总结了热液流体包裹体年代学，氧同位素找矿模式，同位素分馏及其影响，ＣＯ２、Ｈ２－Ｈ２Ｏ平衡法测定水的氢氧同位素组成及稳定同位素分析实验研究等，并应用这些方法研究了康滇...     

研究了地下水中HCO^—3来源的稳定碳同位素法

自然界中ＣＯ２主要来自有机质、大气和碳酸盐岩石，因同位素分馏作用，其稳定碳同位素组成在这三种物质中的分配不尽相同。本文根据地下水实测ＨＣＯ＾－３的δ＾１３Ｃ＾②值，利用热力学及同位素平衡计算与之相平衡的ＣＯ２气体的δ＾１３Ｃ值，确定了ＣＯ２气体来源，进而确定了ＨＣＯ＾－３的有机来源。     

矿物-水体系氢同位素平衡分馏和动力分馏的实验研究

矿物水体系氢同位素平衡分馏系数和动力分馏系数是同位素地球化学研究中的重要参数。这些参数大多由实验测定。氢同位素分馏的实验研究主要包括矿物水体系氢同位素交换实验,交换实验前后矿物、水的氢同位素分析及分馏机理、平衡分馏、动力分馏理论研究。为确保氢同位素分馏系数和一系列动力学参数的准确可靠,实验中防止氢透过容器壁扩散,避免空气中水汽污染样品,正确控制实验温度等都很重要。本研究以石英管代替前人常用的金（银、铂）管作反应容器,建立了一套实验研究羟基矿物水体系氢同位素平衡分馏和动力分馏的新方法,并开展了电气石水、黑柱石水体系氢同位素分馏的实验研究。所得一系列参数的精度明显好于国外报道的资料。此研究方法可广泛应用于羟基矿物水体系的氢同位素分馏的实验研究。     

氢氧化物族矿物的氧同位素分馏

应用增量方法计算了氢氧化物族矿物的氧同位素分馏,得到常见氢氧化物的18O富集顺序为：褐铁矿＞三水铝石＞针铁矿＞水镁石＞硬水铝石。氢氧化物与其对应的氧化物相比显著地富集18O。三价阳离子的氢氧化物和氧化物的18O富集顺序为：M（OH）3＞MO（OH）＞M2O3。Al（OH）3同质多象变体之间也存在一定的分馏。对于石英-氢氧化物、方解石-氢氧化物和氢氧化物-水体系,本文计算提供了在0-1200℃温度范围内三组内部一致的分馏系数方程。这些理论校准与合成实验结果和／或地表温度下的天然样品相吻合,特别针铁矿、勃姆石和硬水铝石与水之间的氧同位素分馏关系能够满足地质测温的要求。因此,对氢氧化物-水体系的氧同位素分析可望提供表生环境下可靠的地质温度计。     

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.     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

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     

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。     

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.     

Response to the Comment by J. Horita and R.N. Clayton on “The studies of oxygen isotope fractionation between calcium carbonates and water at low temperatures”

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.     

An “On-Line” Method for Oxygen Isotope Exchange Between Gas-Phase CO<Subscript>2</Subscript> and Water

An “on-line” mixing system has been developed and evaluated for continuous oxygen isotope exchange between gas-phase CO₂ and liquid water. The system is composed of three basic parts: equipment and materials used to introduce water and gas into a mixing reservoir, the mixing and exchange reservoir, and a vessel used to separate gas and water phases exiting the system. A series of experiments were performed to monitor the isotope exchange process over a range of temperatures (5–40 °C) and CO₂ partial pressures (202–15,200 Pa). Isotopic exchange was evaluated using CO₂ having δ¹⁸O values of 30.4 and 37.8 ‰ and waters of two distinct oxygen isotope compositions (?6.5 to ?5 and 6 to 7.5 ‰). Isotope ratios were determined by isotope ratio mass spectrometry and cavity ring-down spectroscopy. CO₂ did not reach oxygen isotope equilibrium under the conditions described here. However, oxygen isotope exchange rate constants were determined at different temperatures and regressed to yield the expression k (h^?1) = 0.020 × T (°C) + 0.28. Using this expression, the residence time required to reach oxygen isotope equilibrium may be estimated for a given set of environmental conditions (e.g., δ¹⁸O value of water, temperature). System parameters can be modified to achieve a specific δ¹⁸O value for CO₂. Consequently, the exchange system described here has the ability to deliver a constant flow of CO₂ at a desired oxygen isotope composition. This ability is attractive for a variety of applications such as experiments that utilize flow-through reactors and environmental chambers or require static chemical conditions.     

Quartz-Ferberite Oxygen Isotope Geothermometer and Its Geological Applications

Experiments for oxygen isotope exchange between ferberite and water were carried out and the followingequation on oxygen isotope fractionation between ferberite and water against temperature was obtained:Combining this equation with the equation of Clayton et al. (1972) on oxygen isotope fractionation be-tween quartz and water, an equation on oxygen isotope fractionation between quartz and ferberite was ob-tained:The Bigeleison-Mayer function method was used to calculate the oxygen isotope fractionation betweenquartz and ferberite. The theoretical curve obtained agrees with the experimental calibration results quite wellin the temperature range of study.The above calibrated equation has been used in 5 world famous tungsten deposits to determine their tem-peratures of formation. The results show that the temperature range for an idividual deposit determined by thisgeothermometer agrees with those obtained from fluid inclusion determination and other isotopegeothermometers.     

Oxygen isotope exchange and closure temperatures in cooling rocks

Retrograde exchange of oxygen isotopes between minerals in igneous and metamorphic rocks by means of diffusion is explored using a finite difference computer model, which predicts both the zonation profile of δ¹⁸O within grains, and the bulk δ¹⁸O value of each mineral in the rock. Apparent oxygen isotope equilibrium temperatures that would be observed in these rocks are calculated from the δ¹⁸O values of each mineral pair within the rock. In systems which cool linearly from a sufficiently high temperature or at a low enough cooling rate, such that the final oxygen isotope values are not dependent upon the initial oxygen isotope values ('slow cooling'), the apparent oxygen isotope temperature derived for a rock composed of a single mineral pair can be shown to be simply related to the Dodson closure temperatures ( T _c) for the two phases and the mode of the rock. Adding a third phase into a system which undergoes 'slow' cooling will cause the apparent temperature derived for the two minerals already present to differ from the simple relationship for a two-phase system. In some systems oxygen isotope reversals can be developed. If cooling is not 'slow', then the mineral δ¹⁸O values resulting from cooling will be partly dependent upon the initial temperature of the system concerned. The model successfully simulates the mineral δ¹⁸O values that are often observed in granitic rocks. Application of the model will help in assessing the validity of oxygen isotope thermometry in different geological settings, and allows quantitative prediction of the oxygen isotope fractionations that are developed in cooling closed systems.