对稳定同位素地球化学一个基本原理的反思     

刘耘 《矿物岩石地球化学通报》2007,26(1):49-51

用基于Urey模型的量子化学从头计算,揭示Fe在FeCN63-和FeCN46-中的不同“自旋态”对同位素分馏行为的巨大影响,说明了只考虑“价态”的做法是不正确的,修正了关于“重同位素倾向于富集在高价化合物中”的这个广泛被接受的基本原理。并首次指出在压力导致自旋态变化的地质过程中,必定存在同位素分馏反常的复杂状况,是值得进一步研究的方向。  相似文献   

高硒环境样品中硒的形态分析方法   总被引：2，自引：0，他引：2  

朱建明  秦海波  李璐  魏中青  雷磊  苏宏灿 《矿物岩石地球化学通报》2007,26(3):209-213

在恩施富硒碳质岩和土壤样品中硒矿物学研究的基础上,提出了硒连续化学提取的改进方案。化学操作上定义为7个连续步骤:水溶态(MQ水提取)、可交换态(0.1 mol/L的K2HPO4 KH2PO4,pH=7.0)、有机结合态(0.1 mol/L NaOH)、元素态(1 mol/L Na2SO3溶液)、酸溶性提取态(15%CH3CO2H溶液)、硫化物/硒化物态(1 mol/L CrCl2 HCl溶液)和残渣态硒(HNO3 HF H2O2混合消化液)。使用HG-AFS法检测了各结合态中的硒形态和总硒,上述流程提取硒加和与总硒间显著一致,平均回收率为99.2%,符合平行样品间变异系数低于10%的精度要求。该方法简单易行,能够准确地揭示富硒地质样品中硒的形态信息。  相似文献   

微生物降解有机物的碳氢同位素分馏研究进展     

王万春 《矿物岩石地球化学通报》2007,26(3):269-275

微生物降解使有机化合物的稳定碳、氢同位素发生不同程度分馏的研究在有机污染物来源和微生物环境修复等领域取得了长足进展,并对原油和天然气微生物降解研究有借鉴意义。微生物作用下的同位素分馏为动力同位素分馏,导致重同位素在残余物中富集。影响微生物降解有机物同位素分馏的主要因素有微生物的降解代谢途径、辅酶作用、降解类型与程度、同位素质量差异和有机物碳数等。不同的微生物代谢途径代表不同的生物化学反应,造成了同位素分馏的显著差异;辅酶对反应的催化作用使微生物作用造成的同位素分馏更加复杂。低碳数正构烷烃遭受微生物降解程度越高,碳、氢同位素的分馏也越大,同位素变重与降解程度之间有明显的相关性。但对于复杂化合物,由于降解的多级反应,同位素分馏与降解程度间的相关性并不明显。在同样降解程度下,氢同位素分馏大于碳同位素分馏,低碳数正构烷烃的同位素分馏大于高碳数正构烷烃的同位素分馏。  相似文献   

氢氧化物族矿物的氧同位素分馏   总被引：2，自引：0，他引：2  

郑永飞  徐宝龙 《地球化学》1998,27(2):141-152

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。  相似文献   

Oxygen isotope fractionation in mantle minerals     

Yongfei Zheng  Chunsheng Wei  Gentao Zhou  Baolong Xu 《中国科学D辑(英文版)》1998,41(1):95-103

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of¹⁸O-enrichment:pyroxene (Mg, Fe, Ca)₂Si₂O₆>olivine (Mg, Fe)₂SiO₄ > spinel (Mg, Fe)₂SiO₄> ilmenite (Mg, Fe, Ca) SiO₃>perovskite (Mg, Fe, Ca) SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) System are in excellent agreement with the experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle might result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth’s interior can be described by the following sequence of¹⁸O-enrichment:upper crust>lower crust>upper mantle>transition zone>lower mantle>core. Project supported by the National Natural Science Foundation of China and the Chinese Academy of Sciences.  相似文献   

A Coupled Riverine-Marine Fractionation Model for Dissolved Rare Earths and Yttrium     

Robert H. Byrne  Xuewu Liu 《Aquatic Geochemistry》1998,4(1):103-121

Fractionation of yttrium (Y) and the rare earth elements (REEs) begins in riverine systems and continues in estuaries and the ocean. Models of yttrium and rare earth (YREE) distributions in seawater must therefore consider the fractionation of these elements in both marine and riverine systems. In this work we develop a coupled riverine/marine fractionation model for dissolved rare earths and yttrium, and apply this model to calculations of marine YREE fractionation for a simple two-box (riverine/marine) geochemical system. Shale-normalized YREE concentrations in seawater can be expressed in terms of fractionation factors ( _ij ) appropriate to riverine environments ( ) and seawater ( ): where and are input-normalized total metal concentrations in seawater and is the ratio of total dissolved Y in riverwater before and after commencement of riverine metal scavenging processes. The fractionation factors ( _ij ) are calculated relative to the reference element, yttrium, and reflect a balance between solution and surface complexation of the rare earths and yttrium.  相似文献   

大豆蛋白废水处理中泡沫分离过程的数学模型     

杨向平  刘元东  席作家  翟绪丽 《中国海洋大学学报(自然科学版)》2008,38(1):111-115

假设吸附过程始终处于平衡态、气泡大小均一以及每一个气泡均为正十二面体,构建了泡沫分离过程的数学模型.模拟了液池中蛋白质在气液界面上的吸附过程和泡沫层中气泡的失水过程,得出了富集比的表达式,可用于分离效果的预测.经验证,模型与实验条件下的泡沫分离过程基本符合.  相似文献   

Size-fractionated uranium isotopes in surface waters in the Jiulong Estuary in China   总被引：1，自引：1，他引：0  

L&#; E  ZHANG Lei  CHEN Min  QIU Yusheng  XING N  YANG Weifeng  LI Yanping  HUANG Yipu 《海洋学报(英文版)》2008,27(1):29-41

Surface water was collected from the Jiulong Estuary for determination of activity concentrations of uranium isotopes in different size fractions, namely, greater than 53, 10 -53, 2 - 10, 0.4 -2 μm, 10 000 u -0.4 μm and less than 10 000 u fractions by microfihration and cross-flow uhrafiltration technologies. Results indicated that most of the dissolved uranium （ 〈 0.4 μm） exis- ted in the low molecular mass fraction （ 〈 10 000 u）, and the colloidal uranium-238 （10 000 u -0.4 μm） only contributed less than 1% of the dissolved uranium-238. The fractions of colloidal uranium in the dissolved phases decreased with the increasing sa- linity. A positive linear relationship between uranium-238 activities and salinities was observed for the dissolved, colloidal and low molecular mass fractions, indicating a conservative behavior of uranium in the Jiulong Estuary. In the particulate phases （ 〉 0.4 μm）, the partitioning of uranium isotopes among different size fractions was controlled by the partitioning of particle concentrations. In the regions with salinities below 20, the partitioning of uranium-238 among different size fractions was as follows： 10 - 53 μm 〉 2 - 10 μm 〉 0.4 - 2 μm greater than above 53 μm. However, the order at the offshore station with salinities above 30 changed as follows ： 0.4 - 2 μm 〉 10 - 53 μm 〉 2 - 10 μm greater than above 53 μm. The fraction of the 0.4 - 2 μm particles increased at the offshore station, suggesting the increased contribution of the authigenic uranium. The activity ratio of uranium-234 to uranium-238 in the dissolved phases, including the low molecular mass fraction and the colloidal fraction, was larger than unity, showing the occurrence of excess uranium-234. In contrast, the activity ratio of uranium-234 to uranium-238 in all size fractions of the particulate phase was close to the equilibrium value （1.0）. The observed different values of the activity ratio of uranium-234 to uranium-238 in the dissolved phase and the partic  相似文献   

微量水δ(~(17)O)和δ(~(18)O)CoF_3法线外同时测试新技术     

余婷婷  甘义群  刘存富  李小倩  刘运德  蔡鹤生  周爱国  周建伟 《地质科技情报》2010,29(1)

三氧同位素(16O、17O、18O)组成特征可有效示踪天然水循环及其环境效应,微量水δ(17O)和δ(18O)CoF3法同时测试新技术的建立,可为三氧同位素定量研究提供有效的分析手段,特别是能够捕捉到像光合作用、呼吸作用等生物过程中发生的同位素分馏现象。在国内首次建立了微量水δ(17O)和δ(18O)CoF3法线外同时测试新技术,样品量仅需2μL,整个制样时间约40min。采用在质谱测试前对待测样品在100℃下预热10 min,待O2完全解吸后再进行质谱测试的方法,避免了制样和测试过程中的记忆效应及分馏效应,δ(17O)和δ(18O)的分析精度分别达到±0.07‰和±0.14‰。该法使用固体试剂CoF3替代了剧毒的气态氟化物BrF5,使得制样流程更加安全可靠且样品量少,适用性强,具有很大的推广应用价值。  相似文献   

Behavior of REE Fractionation during Weathering of Dolomite Regolith Profile in Southwest China   总被引：3，自引：0，他引：3  

GONG Qingjie  ZHANG Gaixi  ZHANG Jing  JIANG Biao  MA Nan 《《地质学报》英文版》2010,84(6):1439-1447

<正>REE fractionation during the weathering of dolomite has been recognized for decades.A regolith profile on dolomite in southwest Yunnan of China was selected to investigate the behaviors of REE during weathering.The weathering of dolomite is divided into two stages:the pedogenesis stage and soil evolution stage,corresponding to the saprolites and soils respectively in the regolith profile. SiO_2,TiO_2,P_2O_5,Zr,Hf,Nb and Ta were immobile components during the weathering by and large, while Al_2O_3,K_2O and Fe_2O_3 were lost during the soil evolution stage in the physical form(clay minerals probably).REE were fractionated during the whole weathering of dolomite.The field weathering profile and the lab acid-leaching experiments on dolomite indicate that MREE were enriched clearly relative to other REE during the pedogenesis stage in a "capillary ascending-adsorption" mechanism, but they did not fractionate clearly in the soil evolution stage.REE were lost and accumulated in the weathering front of dolomite during the soil evolution stage in a "physical-chemical leaching" mechanism.  相似文献