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1.
采用密度泛函方法计算了水溶液中B(OH)3和B(OH)4-间硼同位素的平衡分馏参数。在模拟液相环境时,采用基于分子簇模型的"水滴"法,分别以6、12、18、24和30个水分子环绕兴趣分子的方式构建"水滴"。对纯水体系的计算结果显示该分馏参数在25?C时为1.031,与实验测定值吻合地非常理想。对不同个数水分子所形成的液相构型进行比较,发现在计算硼同位素的分馏时,12个水分子的"水滴"构型是比较经济和准确的建模方式。此外,我们还讨论了前人对该体系分馏计算中存在的不足,并提出了将分子簇模型扩展到碳酸盐矿物形成过程中硼同位素分馏研究的可能。 相似文献
2.
PHVA在简化模型大小,提高计算效率在计算科学有重要的地位.应用PHVA方法可以求分子簇模型兴趣区的简谐频率,可以用来研究超大分子或矿物的局部振动性质,可用于化学反应动力学及同位素分馏系数计算等. 相似文献
3.
硫化物是重要的矿物类,通常是一个或多个金属元素与硫结合而形成硫化物.硫化物作为大多数金属的主要来源具有重大的经济利用价值,硫化物中硫同位素分馏的研究一直是同位素地球化学研究的热点.研究不同金属硫化物之间的硫同位素分馏效应,对于利用硫同位素对成矿作用过程和成矿物质来源开展地球化学示踪,具有非常重要的意义.本文结合笔者近期的工作概述了硫化物中硫同位素分馏的理论计算研究,认为虽然半经验半理论的增量方法在同位素分馏计算中存在一定的局限性,但在没有其他实用的理论计算方法时,改进的增量方法可以作为硫化物中硫同位素分馏计算的一种理论估算方法. 相似文献
4.
刘耘 《矿物岩石地球化学通报》2021,40(6):1287-1303
近十年来,国内稳定同位素地球化学的理论解释已普遍达到了量子化学水平.基于精密的量子化学从头或第一性原理,研究者们开始了平衡和动力学分馏系数的计算.在同位素的分析测试、野外观察、理论和计算四个方向上,国内在理论和计算方向的发展可能还算最好的,整体处于国际第一方阵的地位.国内学者率先发展了超冷体系同位素分馏、含压力效应的同位素分馏、同位素的浓度效应、团簇同位素、微小同位素异常、热梯度下同位素扩散效应、高温重复过程等方向的同位素理论和计算方法,也发展了针对固-液两相同位素分馏的可变体积的分子簇(VVCM)计算新方法、针对重金属同位素固相体系的含核体积效应处理的方法,以及针对熔体中同位素扩散的动力学分馏的理论和计算方法.同时,还为大量不同的非传统(金属)同位素体系,提供了大量的平衡分馏系数,为这些同位素体系的日后深入应用奠定了较好的基础.但是,在这些成果中,真正由我国学者首先提出的原始概念、模型、体系和方法还很少,绝大多数都是对前人(主要是国外同行)提出的理论体系和新兴发展方向的修改和补充.未来我国同位素理论和计算领域应率先使用包含量子场论在内的新一代理论工具,在同位素效应的新方向、新概念的提出和新理论的建立方面,做出更多的贡献. 相似文献
5.
利用氧键计算兰晶石、十字石等矿物的氧同位素分馏方程 总被引：2，自引：0，他引：2
矿物的同位素分馏方程是同位素地球化学研究的重要基础。因此,人们对分馏方程的研究一直十分重视。但是,许多常见的矿物至今还没有有效的氧同位素分馏方程。这与有些矿物不但很难用实验方法测定其分馏方程,而且很难用热力学方程进行有效的理论计算有关。 相似文献
6.
制约高温过程中Ca同位素研究的因素主要有分析技术、储库端元和分馏机理.随着质谱的发展和双稀释剂的应用,分析技术已经能很好地满足高温过程同位素示踪的要求,但是目前对于储库端元的研究还比较薄弱,而分馏机理也存在较大争议.因此,完善不同储库端元的Ca同位素组成,厘清Ca同位素分馏机理势在必行.全硅酸岩地球作为最重要的Ca储库,前人研究表明,其Ca同位素组成在0.94‰～1.05‰之间变化.Ca—O化学键能的强弱是造成矿物间Ca同位素组成差异的主要因素,此外,温度和矿物组成差异也会引发Ca同位素分馏.热扩散和化学扩散都会引起Ca同位素分馏,但热扩散只发生在特殊的环境中.化学扩散受控于CaO化学势梯度,而化学势梯度受控于体系的成分、温度和压力.部分熔融和熔体提取过程中轻同位素趋向于富集在熔体相中.由于不同含钙矿物的Ca同位素组成存在差异,因此,在分离结晶过程中,矿物晶出顺序不同会引起Ca同位素分馏.变质作用过程中流体交代作用或碳酸盐岩沉淀都会造成Ca同位素分馏.K-Ca衰变体系使得Ca同位素既可以对古老的富钾岩石或矿物进行定年,也可以利用放射性成因Ca对源区和壳幔物质循环进行示踪. 相似文献
7.
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
8.
碳酸钙-水体系氧同位素分馏系数的低温实验研究 总被引：4，自引：0，他引：4
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。 相似文献
9.
采用密度泛函方法模拟了阳离子对水体中B(OH)3和B(OH)4-的影响,计算海水的硼同位素平衡分馏参数。模拟海水环境时,选择基于分子簇模型的"水滴"法,以最多12个水分子环绕兴趣分子的方式构建"水滴"。对海水环境的计算结果显示,B(OH)3和B(OH)4-的硼同位素平衡分馏系数在25?C时为1.031,与纯水环境下的该分馏值并无明显差别。研究表明前人对B(OH)3和B(OH)4-间硼同位素平衡分馏参数的实验测定可能存在问题。研究结果为精进硼同位素古环境重建工作和硼同位素平衡分馏测定提供了理论制约。 相似文献
10.
非传统稳定同位素分馏理论及计算 总被引：1，自引：0，他引：1
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。 相似文献
11.
Donald E. Canfield Claus A. Olesen Raymond P. Cox 《Geochimica et cosmochimica acta》2006,70(3):548-561
A synthesis of previous results, which we dub the “standard model,” provides a prediction as to how isotope fractionation during sulfate reduction should respond to physiological variables such as specific rate of sulfate reduction and environmental variables such as substrate availability and temperature. The standard model suggests that isotope fractionation should decrease with increasing specific rates of sulfate reduction (rate per cell). Furthermore, the standard model predicts that low fractionations should be found at both high and low temperatures whereas the highest fractionations should be found in the intermediate temperature range. These fractionation trends are controlled, as a function of temperature, by the balance between the transfer rates of sulfate into and out of the cell and the exchange between the sulfur pools internal to the organism. We test this standard model by conducting experiments on the growth physiology and isotope fractionation, as a function of temperature, by the sulfate-reducing bacterium Desulfovibrio desulfuricans (DSMZ 642). Our results contrast with the “standard model” by showing a positive correlation between specific rates of sulfate reduction and fractionation. Also by contrast with the standard model, we found the highest fractionations at low and high temperatures and the lowest fractionations in the intermediate temperature range. We develop a fractionation model which can be used to explain both our results as well as the results of the “standard model.” Differences in fractionation with temperature relate to differences in the specific temperature response of internal enzyme kinetics as well as the exchange rates of sulfate in and out of the cell. It is expected that the kinetics of these processes will show strain-specific differences. 相似文献
12.
热成因甲烷碳同位素分布的形成机制 总被引：3，自引：1，他引：3
很多学者从不同的角度用不同的方法模拟了从有机母质 (包括煤和干酪根等气源 )形成天然气 (甲烷 )时的碳同位素分馏效应 ,建立了碳同位素分馏效应的很多模型 ,同时也讨论了催化作用和成烃后作用对天然气碳同位素的影响。但这些理论模型和模拟实验结果都还不能完全地拟合自然界中热成因甲烷碳同位素的分布 ,也未能从本质上完全阐明其碳同位素的分馏机制。其原因是各种模型的前提假设都未能完全满足复杂的自然界条件。今后工作的重点应放在用化学动力学的方法建立更完善的模型上 ,同时也应当重点考虑催化作用和成烃后作用对天然气同位素的影响。 相似文献
13.
14.
铜同位素地球化学研究及其在矿床学应用的评述和讨论 总被引：3，自引：0，他引：3
不同地质条件和成矿环境中的铜同位素组成有显著差异,表明利用含铜矿物的铜同位素组成可以作为成矿物质来源的示踪剂.并且,由于铜是主要成矿元素之一,所以铜同位素对于成矿物质来源和成矿过程的示踪更为直接.文章介绍和评述了铜同位素的测试、研究和应用的进展,认为当前对于铜同位素分馏知识的匮乏严重制约着铜同位素研究和应用.从同位素分馏的基本原理出发,提出了铜同位素分馏研究的思路以及可能的分馏规律,对于已发表的部分地质样品测试数据,给出了新的解释,并预测溶解于海水中的铜离子应亏损65Cu. 相似文献
15.
A revised isotope fractionation model for dissimilatory sulfate reduction in sulfate reducing bacteria 总被引：1，自引：0，他引：1
Benjamin Brunner 《Geochimica et cosmochimica acta》2005,69(20):4759-4771
Sulfur isotope fractionation during dissimilatory sulfate reduction has been conceptually described by the widely accepted Rees model as related to the stepwise reduction of sulfate to sulfide within the cells of bacteria. The magnitude of isotope fractionation is determined by the interplay between different reduction steps in a chain of reactions. Here we present a revision of Rees’ model for bacterial sulfate reduction that includes revised fractionation factors for the sulfite-sulfide step and incorporates new forward and reverse steps in the reduction of sulfite to sulfide, as well as exchange of sulfide between the cell and ambient water. With this model we show that in contrast to the Rees model, isotope fractionations well in excess of −46‰ are possible. Therefore, some of the large sulfur isotope fractionations observed in nature can be explained without the need of alternate pathways involving the oxidative sulfur cycle. We use this model to predict that large fractionations should occur under hypersulfidic conditions and where electron acceptor concentrations are limiting. 相似文献
16.
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。 相似文献
17.
Gérard C. Nihous 《Geochimica et cosmochimica acta》2008,72(18):4469-4475
A quantitative model of recent laboratory experiments on carbon isotope fractionation by methane-oxidizing bacteria is proposed. The simulated experimental apparatus consists of a bacterial culture with a constant liquid volume, a gas headspace and a methane bubbling mechanism. The relative effects of bacterial growth and transport phenomena that do not depend on cell density are clarified. In all calculations, gas-liquid mass transfer is defined by unconstrained model parameters. Limited mass transfer from the culture into the headspace, rather than the incomplete dissolution of substrate-rich bubbles, seems to have caused an apparent decrease in the measured carbon isotope fractionation. The experimenters attributed this fractionation shift to a growing imbalance among kinetic rates as methane consumption by bacteria increases. Model predictions support this interpretation but also show that changes in carbon isotope fractionation in the course of the experiments cannot be unambiguously correlated with bacterial cell density unless gas-liquid mass transfer parameters are calibrated. Simulations of other laboratory experiments indicate that a reported change in carbon isotope fractionation could, in part at least, be the result of experimental conditions rather than the emergence of a different methane oxidation pathway postulated by the experimenters. A careful evaluation of mass transfer from the liquid culture into the gas headspace is warranted in this type of experiments since isotope fractionation factors are likely to be used in a wide variety of environmental contexts. 相似文献
18.
The advent of multiple collector-inductively coupled plasma-mass spectrometry has provided an impetus to the study of isotope abundance variations in natural materials. In particular, the study of "non-traditional" stable isotopes has revealed isotope fractionation variations caused by a range of physiochemical and biological mechanisms. The magnitude of these variations may be < 1 per mil per mass unit, but are significant in terms of the experimental uncertainties involved, provided rigorous mass spectrometric protocols are followed. The double spike technique can be used effectively to evaluate isotope fractionation effects for both multiple collector-inductively coupled plasma-mass spectrometry and thermal ionisation mass spectrometry. The demanding nature of this research implies the need for internationally-accepted reference materials so that interlaboratory comparisons can be made with confidence. At present, isotopically certified reference materials are unavailable for many elements, including Cu, Zn, Mo and Cd, and it is important that this situation be rectified as soon as practicable. Until such time as isotopically certified reference materials become available for every element, stable isotope geochemists should adopt a common reference material as the standard for each element so that rigorous interlaboratory comparisons can be made. 相似文献
19.
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。 相似文献
20.
Yunyan Ni Geoffrey S. Ellis Barry Katz Yongchun Tang 《Geochimica et cosmochimica acta》2011,75(10):2696-2707
Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane. 相似文献