非传统稳定同位素分馏理论及计算

综述了稳定同位素平衡和动力学分馏的一些主要的理论方法。首先介绍了平衡分馏的理论方法,从平衡分馏的核心理论-Bigeleisen Mayer公式(或称Urey模型)以及对它的一些高级能量校正开始,介绍了基于路径积分的分子动力学方法和蒙特卡罗方法对同位素非谐效应的处理,介绍了压力效应的理论计算方法,最后介绍了核体积效应及其理论计算方法,并强调核体积效应是未来重金属同位素研究的重要部分。另外,综述了同位素动力学分馏的主要理论和计算方法,首先介绍了在稳态下因温度梯度引发的同位素分馏,着重介绍了基于局部热力学平衡理论的计算方法和最新结果;然后从如何使用过渡态理论计算化学反应导致的同位素动力学分馏出发,深入介绍了磁同位素效应和由于核体积效应引发的异常同位素动力学分馏;然后对低温下矿物生长的同位素动力学理论模型进行了介绍,尤其是仔细介绍了其中DePaolo的表面动力学模型,并对由吸附和共沉降过程产生的动力学分馏也进行了介绍。最后详细介绍了在气化过程、固体中、高温硅酸洋熔体中由于扩散引起的同位素动力学分馏,以及如何对这些过程进行理论处理,强调了开展固体矿物扩散理论计算的重要性。     

扩散法——EA-IRMS测定天然水体铵态氮同位素实验条件研究

稳定氮同位素是研究氮循环和氮污染源示踪的一个有效手段。然而目前国内对水体中铵态氮同位素测定方法研究较少,限制了水体氮循环和污染机理的深入探讨。本文采用改进的扩散法(EA-IRMS)测定水中铵态氮同位素,探讨了样品制备过程中扩散溶液的体积、浓度和扩散时间对回收率及氮同位素测定值的影响。实验得出最佳扩散条件为:1.50 mg/L氯化铵溶液400 mL扩散14天,回收率大于95%,且不会产生氮同位素分馏。本研究为高精度测定天然水体中铵态氮同位素提供了更可靠的实验条件。     

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 。     

降水过程中氢氧稳定同位素理论关系研究

大气降水过程中氢氧稳定同位素比值呈现一定的规律,分析了瑞利分馏中分馏系数的影响因子,基于瑞利分馏原理和质量守恒定律,分别推导了开放系统和封闭系统降水过程中的稳定同位素微分方程模型,研究了大气降水过程中氢、氧稳定同位素变化规律,导出了云团水汽和降水氢、氧之间的相互关系,结果表明这一关系并非简单的线性关系。     

低温环境下Zn同位素分馏的若干重要过程

锌同位素是一种新的地球化学示踪剂,详细了解锌同位素分馏过程与机理是运用其解决科学问题的关键.本文对前人研究的吸附、沉淀、扩散、还原、生物过程中的锌同位素分馏研究结果进行了系统总结.在沉淀过程中.沉淀富集轻同位素;随着扩散距离增加,溶液Zn同位素组成变轻;还原生成的金属Zn富集轻同位素;在生物参与的Zn地球化学循环过程中,硅藻表面吸附重同位素,但生物本身优先利用轻同位素.     

汞的稳定同位素分馏机理

汞是唯一能够以气态单质形式进行长距离传输的有毒重金属元素,其环境行为和健康危害受到广泛关注.近十多年来发展起来的汞稳定同位素技术为研究环境中汞的来源、迁移转化过程以及相应的生态环境效应提供了新的视野.汞同位素是自然界中唯一表现出多种显著非质量分馏(MIF)的独特金属同位素体系,对汞同位素的研究一直偏重应用,而对其分馏机理的认识十分有限.本文从汞稳定同位素分馏理论、分馏实验研究和实际环境过程的汞同位素分馏三方面系统阐述了近十多年来关于汞同位素分馏机理的研究成果、最新进展和未来发展方向.尽管目前的研究普遍认为无机汞的光化学氧化还原和甲基汞的光化学降解是环境中汞同位素MIF的主要产生机制,然而MIF程度和方向的影响因素还不完全清楚,其量化理论还未完全建立,实际环境过程中的分馏机理研究还相对缺乏.未来需要结合理论和实验研究进一步明确大气、陆地、海洋、极地、古环境等实际环境体系中的汞同位素分馏机理,进而拓展汞同位素的应用.     

氩同位素分馏的实验研究

尽管⁴⁰Ar和36Ar之间质量相差达1/10,但是受放射性成因⁴⁰Ar的影响,一般认为难以进行氩同位素分馏研究.本文通过自行设计的一套氩扩散迁移实验分析系统,对比研究了氩在不同的扩散介质条件下扩散迁移前后氩同位素组成变化情况,证实氩在致密的扩散介质条件下以分子流形式从一个储库向另一个储库的迁移过程中,由于36Ar和⁴⁰Ar的迁移速率不同,扩散后的⁴⁰Ar/36Ar值比扩散前的值要小,也即发生了氩同位素分馏.氩同位素分馏的特征表现为最初的一段时间内分馏程度逐步增强,在一定时间后,由于储库之间压力逐渐达到平衡,分馏程度逐步减小.研究自然界中存在的氩同位素分馏,不仅可以判别油气田中油气运移的方向、增强油气远景评价和地球化学勘探,而且对深源岩浆的起源、迁移等研究也可提供新的研究思路和途径.     

蒸发过程中水体稳定同位素富集与空气湿度的关系

通过同位素分馏模型的物理意义分析及实验模拟分析,探讨空气湿度对蒸发过程水体稳定同位素富集过程的影响机理,研究认为:1空气相对湿度决定了扩散系数和自由空气同位素组成对分馏系数的影响比例,空气相对湿度越小,分馏系数受扩散分馏系数影响越大,分馏系数受自由空气水汽同位素组成影响则越小,反之亦然;2空气相对湿度与蒸发残余水体氢氧稳定同位素富集程度具有负相关性,即空气湿度越大越不利于残余水体重同位素富集;3模拟残余水体同位素丰度对空气相对湿度的敏感性呈负指数关系。在无外界气态水介入的蒸发实验中,残余系数为0.194条件下,当相对湿度小于80%时,H、O稳定同位素模拟结果对湿度的敏感性均小于0.0002,即相对湿度变化对模拟残余水体同位素丰度影响很小;当湿度大于80%时,湿度变化对模拟结果的影响呈指数关系急剧增加,湿度大于80%的蒸发实验需要准确观测相对湿度值。     

本期文章导读

正非传统稳定同位素地球化学的建立与发展是本世纪地球化学领域的重要进展之一。镉(Cd)同位素分馏主要发生在蒸发/冷凝过程、无机吸附/沉淀过程及生物吸收利用过程。这些Cd同位素分馏效应被成功应用于构建海洋生物地球化学Cd循环体系、反演古海洋环境及初级生产力变化,硫化物矿床成矿流体演化、成矿物质来源示踪及不同成因矿床类型判别研究,环境体系Cd污染源的源区判别、农田面源Cd来源及其运移、循环及储存机制研究。在海洋科学、地球科学、环境科学及农业科学研究上展现出巨大的应用潜力。该文提出下一步应深入开展高精度Cd同位素分析方法研究,探讨Cd同位素分馏机制和分馏模型,尤其是应深入研究微生物作用下Cd同位素分馏效应,建立Cd同位素生物分馏地球化学示踪体系,推动非传统稳定同位素地球化学创新发展。     

硝酸盐氮氧稳定同位素分馏过程记录的海洋氮循环研究进展

海洋生态系统中的氮素生物地球化学循环主要是由微生物的代谢过程来驱动的,包括氮固定、氮同化、硝化以及反硝化和厌氧氨氧化过程,这些过程都伴随着不同程度的氮氧同位素的分馏,直接影响着海洋硝酸盐中的氮氧稳定同位素组成.因此,通过检测海洋硝酸盐中的氮氧稳定同位素信号,就可以捕捉到海洋中发生的具体氮素循环过程.细菌反硝化法是这一研究最有力的手段,通过细菌的作用把硝酸盐中记录的氮氧稳定同位素信号转化到N2O中,再通过痕量N2O的同位素质谱测定和分析,准确地反映海洋中发生的氮素转化过程.硝酸盐氮氧稳定同位素分馏过程为深入理解海洋氮循环提供了一个重要的工具,有力推动了海洋氮素生物地球化学的研究,在近10年来取得了重要进展.     

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the ¹²CH₄ and ¹³CH₄ species, respectively, have been calculated.Compared with the carbon isotopic composition of the source methane (δ¹³C₁ = −39.1‰), a significant depletion of the heavier carbon isotope (¹³C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ¹³C_diff −δ¹³C_source) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the ¹²CH₄ and ¹³CH₄ entities. No measurable solubility fractionation was observed.The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous “semi-infinite” shale caprock over a period of 10 Ma.In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas.The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.     

Fe-Cu-Zn-Mo同位素示踪氧化还原过程

非传统稳定同位素（Fe-Cu-Zn-Mo）理论与数据相结合提高了科研工作者对地质体系氧化还原过程的理解。本文对这一相对较新的领域进行了综述,包括与氧化还原过程相关的同位素分馏理论和实验约束、时空尺度下的氧逸度以及同位素示踪氧化还原过程。稳定同位素理论预测,Fe-Cu-Zn-Mo同位素应该对氧化还原状态的变化能够做出响应。结果表明,Fe同位素作为岩浆过程、表生过程、俯冲带流体性质"氧逸度计"应用前景广阔;Cu同位素在岩浆、热液、陆地系统可以很好地示踪氧化还原过程;Zn同位素由于络合过程分馏已经被用在许多不同环境中作为含硫/碳流体迁移的敏感示踪剂;Mo同位素作为古氧逸度计可有效重建古海洋-大气氧化还原状态。     

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。     

The effect of aqueous diffusion on the fractionation of chlorine and bromine stable isotopes

Diffusive isotopic fractionation factors are important in order to understand natural processes and have practical application in radioactive waste storage and carbon dioxide sequestration. We determined the isotope fractionation factors and the effective diffusion coefficients of chloride and bromide ions during aqueous diffusion in polyacrylamide gel. Diffusion was determined as functions of temperature, time and concentration. The effect of temperature is relatively large on the diffusion coefficient (D) but only small on isotope fractionation. For chlorine, the ratio, D_³⁵Cl/D_³⁷Cl varied from 1.00128 ± 0.00017 (1σ) at 2 °C to 1.00192 ± 0.00015 at 80 °C. For bromine, D_⁷⁹Br/D_⁸¹Br varied from 1.00098 ± 0.00009 at 2 °C to 1.0064 ± 0.00013 at 21 °C and 1.00078 ± 0.00018 (1σ) at 80 °C. There were no significant effects on the isotope fractionation due to concentration. The lack of sensitivity of the diffusive isotope fractionation to anything at the most common temperatures (0 to 30 °C) makes it particularly valuable for application to understanding processes in geological environments and an important natural tracer in order to understand fluid transport processes.     

The significance of isotope specific diffusion coefficients for reaction-transport models of sulfate reduction in marine sediments

Modeling isotopic signatures in systems affected by diffusion, advection, and a reaction which modifies the isotopic abundance of a given species, is a discipline in its infancy. Traditionally, much emphasis has been placed on kinetic isotope effects during biochemical reactions, while isotope effects caused by isotope specific diffusion coefficients have been neglected. A recent study by Donahue et al. (2008) suggested that transport related isotope effects may be of similar magnitude as microbially mediated isotope effects. Although it was later shown that the assumed differences in the isotope specific diffusion coefficients were probably overstated by one or two orders of magnitude (Bourg, 2008), this study raises several important issues: (1) Is it possible to directly calculate isotopic enrichment factors from measured concentration data without modeling the respective system? (2) Do changes in porosity and advection velocity modulate the influence of isotope specific diffusion coefficients on the fractionation factor α? (3) If one has no a priori knowledge whether diffusion coefficients are isotope specific or not, what is the nature and magnitude of the error introduced by either assumption? Here we argue (A) That the direct substitution of measured data into a differential equation is problematic and cannot be used as a replacement for a reaction-transport model; (B) That the transport related fractionation scales linearly with the difference between the respective diffusion coefficients of a given isotope system, but depends in a complex non-linear way on the interplay between advection velocity, and downcore changes of temperature and porosity. Last but not least, we argue that the influence of isotope specific diffusion coefficients on microbially mediated sulfate reduction in typical marine sediments is considerably smaller than the error associated with the determination of the fractionation factor.     

Liquid composition-dependence of calcium isotope fractionation during diffusion in molten silicates

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but ⁴⁴Ca/⁴⁰Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al₂O₃, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.     

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。     

Numerical estimation of effective diffusion coefficients for charged porous materials based on micro-scale analyses

In order to describe diffusive transport of solutes through a porous material, estimation of effective diffusion coefficients is required. It has been shown theoretically that in the case of uncharged porous materials the effective diffusion coefficient of solutes is a function of the pore morphology of the material and can be described by the tortuosity (tensor) (Bear, 1988 [1]). Given detailed information of the pore geometry at the micro-scale the tortuosity of different materials can be accurately estimated using homogenization procedures. However, many engineering materials (e.g., clays and shales) are characterized by electrical surface charges on particles of the porous material which strongly affect the (diffusive) transport properties of ions. For these type of materials, estimation of effective diffusion coefficients have been mostly based on phenomenological equations with no link to underlying micro-scale properties of these charged materials although a few recent studies have used alternative methods to obtain the diffusion parameters (Jougnot et al., 2009; Pivonka et al., 2009; Revil and Linde, 2006 2, 3 and 4). In this paper we employ a recently proposed up-scaled Poisson–Nernst–Planck type of equation (PNP) and its micro-scale counterpart to estimate effective ion diffusion coefficients in thin charged membranes. We investigate a variety of different pore geometries together with different surface charges on particles. Here, we show that independent of the charges on particles, a (generalized) tortuosity factor can be identified as function of the pore morphology only using the new PNP model. On the other hand, all electro-static interactions of ions and charges on particles can consistently be captured by the ratio of average concentration to effective intrinsic concentration in the macroscopic PNP equations. Using this formulation allows to consistently take into account electrochemical interactions of ions and charges on particles and so excludes any ambiguity generally encountered in phenomenological equations.     

Molecular dynamics simulations of kinetic isotope fractionation during the diffusion of ionic species in liquid water

Interpretation of isotope ratios, a powerful tool in geochemical investigations of fluid-rock systems, requires an understanding of all relevant processes that fractionate isotopes. One such process, diffusion in liquid water, has remained problematic despite its potential significance as a major cause of kinetic isotope fractionation. Recent laboratory experiments published by [Richter, F. M., Mendybaev, R. A., Christensen, J. N., Hutcheon, I. D., Williams, R. W., Sturchio, N. C., and Beloso Jr., A. D. (2006) Kinetic isotopic fractionation during diffusion of ionic species in water. Geochim. Cosmochim. Acta70, 277-289.] have shown clearly for the first time that lithium and chloride isotopes are fractionated by diffusion in liquid water, whereas magnesium isotopes are not. In the present paper, we present the results of molecular dynamics simulations of lithium, chloride, and magnesium diffusion in liquid water that were designed to provide molecular-scale insight into the experimental findings of Richter et al. (2006). Our results indicate that the self-diffusion coefficients of lithium, chloride, and magnesium isotopes follow an inverse power-law dependence on ion mass (, where D_i is the self-diffusion coefficient of a solute with isotopic mass m_i). The power-law exponents (β) deduced for lithium, chloride, and magnesium from the diffusivity data of Richter et al. (2006) are consistent with the mass dependencies found in our simulations. Further analysis of our simulation results showed that the experimental β-values are inversely related to the residence times of water molecules in the first solvation shells of the diffusing ions, as expected from mode-coupling and renormalized kinetic theories.