生物气CO_2还原途径中碳同位素分馏作用研究及应用

地质历史中,CO2/H2还原产甲烷作用对生物气的形成具有十分重要的意义。中国柴达木盆地第四系生物气主要为CO2/H2还原型生物气。笔者以CO2/H2还原生气理论为指导,进行不同初始碳同位素值和不同赋存状态碳源的生物模拟实验,研究CO2/H2还原产气过程中发生的碳同位素分馏作用。实验结果表明,产物中δ13CH4值与底物的δ13C值呈很好的正相关关系;在反应母质过量的情况下,碳源的赋存状态可以影响产物甲烷的碳同位素组成。以游离形式CO2还原产生的甲烷δ13C值,相对于以HCO3-、CO23-离子形式产生的甲烷δ13C值轻。通过柴达木盆地东部第四系生物气田实例分析,探讨了该区生物气的主要底物CO2的来源及赋存状态,对评价盆地生物气资源和有利勘探区预测有重要的参考价值。     

天然气溶解过程中组分分馏模型及其应用

天然气不同组分在水中溶解度的差异,导致溶解相与残留游离相天然气组分组成不同,即发生组分的溶解分馏效应。溶解分馏效应在天然气水溶运移、溶解散失等过程中均有发生。揭示天然气组分的溶解分馏规律、建立定量分馏模型,有助于天然气气源对比和成藏过程示踪。以Henry定律为依据,对不同组分溶解特征分析,提出了溶解度分数的概念,并建立了溶解分馏模型。根据该模型和各组分的溶解度分数和天然气溶解量,可计算各组分的溶解分馏量,恢复天然气初始组成特征。计算表明,威远震旦系气藏初期的天然气组成为:CH4为72.70%,C2H6为0.09%,CO2为22.41%,N2为4.07%,干燥系数(C1/C1-5)为99.876%。溶解作用使天然气中CO2含量显著降低,烃类气体含量增加,而天然气干燥系数降低。结果有助于天然气成因判识和气源对比等。     

内蒙古敖包吐萤石矿床地质和地球化学特征

笔者总结了敖包吐萤石矿床的地质特征,并通过萤石的稀土元素的地球化学和Nd同位素研究,探讨了该矿床的成矿作用和成矿物质来源。敖包吐萤石矿床产出于下二叠统大石寨组火山—沉积岩与燕山中期花岗岩的接触带,为单一萤石矿床。萤石矿石的稀土元素的含量(∑REE)变化范围为(8.04～30.04)×10-6,平均为19.42×10-6;轻重稀土LREE/HREE值0.24～0.65,平均0.52;LaN/YbN为0.07～0.62,平均0.26;δEu为0.42～0.90,平均0.60,具Eu负异常和明显重稀土富集的特征。岩矿石的Nd同位素研究表明,萤石矿石的εNd(t)都表现为很大的负值,以成矿主期年龄138Ma计算的εNd(138Ma)为-7.30～-30.55,具有古陆壳的演化特征,暗示其成矿的物质来源主要是壳源物质。在Moller的Tb/La-Tb/Ca成因判别图解中,敖包吐矿床的萤石的结晶作用表现为重新活化的趋势,反映流体具有混源的特征,既有热液成因,又有沉积成因。二叠世的海相火山活动通过海底喷气和喷流的作用形成了初始矿源层,而燕山中期花岗岩浆的侵位与结晶分异,又对初始矿源层的活化和富集提供了流体和热能的来源。成矿流体在经历了长期的演化后在大石寨组的构造薄弱破碎的的部位沉淀析出,形成敖包吐萤石矿床。     

天然水铬污染与其同位素组成的相关性研究

Cr(Ⅵ)作为水体中重要的污染物质,其同位素组成对水体环境变化具有较强的敏感性.铬在氧化还原过程中产生明显的同位素分馏作用,根据水体中铬的同位素组成可指示水环境中Cr(Ⅵ)的还原程度.笔者以黄石某无机盐厂周围污染水体为例,对天然水体中的铬污染及其同位素组成的相关性进行了分析研究.     

Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

江西省安福地区地热水化学特征研究

为研究江西安福地区水文地球化学特征及控制因素, 本文采集了15组样品, 采用水化学、同位素分析等方法进行研究。结果表明: 研究区地热水以Na-HCO3型水为主, 地下水以HCO3-Na·Ca型为主, 地表水由西南向东北从HCO3-Na·Ca向HCO3-Ca型水演化。水化学组分演化过程主要受岩石风化作用控制, 地层封闭性较差, 水中的Na+、HCO– 3、Sr2+来源于硅酸岩风化溶解。由稳定同位素特征可知, 研究区地热水补给来源为大气降水。研究区热储温度为49.8~101.4 ℃, 地热水循环深度为1 502.6~1 513.6 m。热水在沿断裂带上升过程中与浅层冷水发生混合, 其混合比例为76.1%~87.5%。研究成果为安福地区水循环演化提供依据, 有利于地热资源的合理开采与保护。     

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。     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.