海洋天然气水合物氢氧同位素分馏初探

天然气水合物的形成会造成氢、氧同位素的分馏.在实验室合成研究中,利用天然海水 [(含 0.03%十二烷基硫酸钠 (SDS)]与甲烷气体反应,通过对水合物生成前后溶液中的 Cl-的质量浓度和氢、氧同位素组成的测定,研究了天然气水合物生成过程中氢、氧同位素的分馏情况.实验证明氢、氧的重同位素易于富集在水合物中,其在天然海水-甲烷体系中的分馏系数分别为 1.018～ 1.036和 1.003 4～ 1.006 3,这一分馏系数稍大于前人在纯水和 NaCl溶液中所测得的分馏系数.     

黑铜矿氧同位素分馏的理论计算

黑铜矿为铜的氧化矿物，对其结构、力场、光谱前人做过较详细的工作。本文在黑铜矿内部力场计算的同位素位移基础上，通过光谱简约配分函数比的计算，得到黑铜矿－水氧同位素分馏方程：１０＾３ｌｈα＝２．５１Ｘ＾２－１４．８７Ｘ＋６．３１（Ｘ＝１０＾３／Ｔ）同时，利用Ｚｈｅｎｇ的加和增量模式法对黑铜矿的氧同位素分馏进行了计算，得到如下黑铜矿－水体系的分馏方程：１０＾３ｌｎα＝２．８９Ｘ＾２－１３．１０Ｘ＋３．９     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

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     

Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos,Greece

Corundum (Crn), including sapphire, occurs in emery pods surrounded by marble on the island of Naxos, Greece. The emery formed from bauxite deposited in karst that was metamorphosed to 400–700°C at 20–15 Ma. Many of these rocks initially appeared well suited for refractory accessory mineral (RAM) thermometry, which uses oxygen isotope fractionation between a RAM – corundum – and a modally dominant phase with faster diffusion of oxygen – calcite (Cc) – to determine peak metamorphic temperatures. However, previous attempts at oxygen isotope thermometry were confounded by highly variable fractionations (Δ¹⁸O) measured at mm-scale and the uncertain calibration of Δ¹⁸O(Cc-Crn) versus temperature. Secondary ion mass spectrometry (SIMS) permits in situ analysis of δ¹⁸O in corundum and calcite at the 10-μm scale in adjacent grains where textures suggest peak metamorphic equilibrium was attained. SIMS analyses of adjacent mineral pairs in eight rocks yield values of Δ(Cc-Crn) that systematically decrease from 7.2 to 2.9‰ at higher metamorphic grade. Pairing these data with independent temperature estimates from mineral isograds yields an empirical calibration of 1,000 lnα(Cc-Crn) = 2.72 ± 0.3 × 10⁶/T² (T in K). The new fractionations (2.7‰ at 1,000 K) are significantly smaller than those calculated from the modified increment method (6.5‰ at 1,000 K; Zheng, Geochimica et Cosmochimica Acta, 1991, 55:2299–2307; Zheng, Mineral Mag, 1994, 58A:1000–1001), which yield unreasonably high temperatures of 630 to 1,140°C when applied to the new Naxos data. The new calibration of Δ(Cc-Crn) can be combined with published fractionations to calculate A-factors for corundum versus a range of 14 other minerals. These new fractionation factors can be used for thermometry or to constrain the genesis of corundum. A compilation of gem corundum δ¹⁸O values shows that many igneous sapphires, including important deposits of basalt-associated sapphire, are mildly elevated in δ¹⁸O relative to the calculated range in equilibrium with mantle values (4.4–5.7‰) and formed from evolved magmas.     

原油运移过程中的氮同位素分馏作用

辽河高升油田和塔里木轮南14井为实例，探索了原油横向和纵向运移过程中氮同位素的分馏作用，初步探讨了原油中含氮有机化合物的运移机制。在莲花油层中，原油沿横向运移约10km后，δ^15N值由12．80‰逐渐变化为11．07‰，下降了1.73‰。在轮南14井由下至上753m厚的五个油层中，原油δ^15N值由0.24‰逐渐变化到－2．92‰，下降了3．19‰。两个实例均表明，原油的运移过程会引起δ^15N值下降。     

岩浆岩体系氧同位素分馏系数的理论计算

The increment method is applied tocalcuation of oxygen isotope fractionation factors for common magmatic rocks by usingoxygen isotope indices for known minerals.The results show that there are some differencesin the degree of 18O-enrichment for the different types of magmatic rocks,andtheir sequence of 18O-enrichment is reckoned as follows acid rocks >neutral rocks > basic rocks > ultrabasic rocks.Two sets of internally consistentfractionation factors for phenocryst-lava systems at temperacture above 1000K and forrock-water systems in the temperature range of 0 to 1200℃ are acquired, respectively.Thetheoretical calibrations are consistent with the data from hydrothermal experiments andempirical estimates.The present results can be used to quantitatively determine thehistory of water-rock exchange and to serve geological thermometry for various magmaticrocks (especially extrusive rocks containing phenocryst).     

Oxygen Isotope Fractionation in TiO2 Polymorphs and Application to Geothermometry of Eclogites

Oxygen isotope fractionation in TiO2 polymorphs has been calculated by the modi-fied increment method .The results that rutile is enriched in ^18O relative to brookite but depleted in ^18O relative to anatase.Due to the same crystal structure ,oxygen isotope partitioning in the TiO2 polymorphs is determined by the cation-oxygen inter-atomic distances.The theoretical calibrations involving rutile are in fair agreement with known experimental measurements and empirical estimates.Application of the theoretic-cal quartz-rutile calibration to geothermometry of natural eclogite assemblages indicates the preservation of isotopic equilibrium at high temperatures.The isotopic temperatures calculated are only slightly lower than the non-isotopic temperatures,indicating the slow rates of exchange for oxygen diffusion in rutile.The kinetics of exchange for oxygen diffu-sion in rutile is accordingly estimated by reconciling the differences between the isotopic and the non-isotopic temperatures.The rates of exchange for oxygen diffusion in rutile should be smaller than those for hornblende,but may be equal to or greater than those for diopside.     

Empirical calibration of oxygen isotope fractionation in zircon

New empirical calibrations for the fractionation of oxygen isotopes among zircon, almandine-rich garnet, titanite, and quartz are combined with experimental values for quartz-grossular. The resulting A-coefficients (‰K²) are:

	Zrc	Alm	Grs	Ttn
Qtz	2.64	2.71	3.03	3.66
Zrc		0.07	0.39	1.02
Alm			0.32	0.95
Grs				0.63

Full-size table

     

不纯碳酸盐碳氧同位素组成的在线分析

利用 GV IsoPrime(R)Ⅱ型稳定同位素质谱仪测量不纯碳酸盐样品的碳氧同位素组成,这些样品是用国家碳酸盐碳氧同位素一级标准物质 GBW04406与去除了碳酸盐的沉积物混合配制而成的, CaCO3含量在 2%～ 90%之间.结果显示 ,δ 13C内部精度为 0.002‰～ 0.005‰ (1σ ),δ 18O内部精度为 0.003‰～ 0.009‰ (1σ ),与测量所得的纯 CaCO3国际国内标准物质结果的内部精度范围一致,且外部精度达到仪器的指标要求,同时 ,不同 CaCO3含量样品的δ 13C和δ 18O的测量值 (测量平均值:δ 13C =-10.932‰± 0.021‰,δ 18O=-12.483‰± 0.054‰; 1σ )也在误差允许范围之内与 GBW04406推荐值 (δ 13C=-10.85‰± 0.05‰, δ 18O =-12.40‰± 0.15‰ ; 1σ )一致.可见碳酸盐的含量并不影响其碳氧同位素组成的分析结果,所以在线分析不纯碳酸盐的碳氧同位素组成是可行的,在线分析不纯碳酸盐样品的碳氧同位素组成之前应先对样品中碳酸盐含量进行大致估计,根据碳酸盐含量高低来确定样品用量以达到最佳分析效果.     

Theoretical calculation of oxygen isotope fractionation factors in carbonate systems

Using established methods of statistical mechanical calculation and a recent compilation of vibrational frequency data, we have computed oxygen isotope reduced partition function ratios (β values) for a large number of carbonate minerals. The oxygen isotope β values of carbonates are inversely correlated to both the mass and radius of the cation bonded to the carbonate anion but neither correlation is good enough to be used as a precise and accurate predictor of β values. There is an approximately 0.6% relative increase in the β values of aragonite per 10 kbar increase in pressure. These estimates of the pressure effect on β values are broadly similar to those deduced previously for calcite using the methods of mineral physics. In comparing the β values of our study with those derived recently from first-principles lattice dynamics calculations, we find near-perfect agreement for calcite and witherite (<0.3% deviation), reasonable agreement for dolomite (<0.9% deviation) and somewhat poorer agreement for aragonite and magnesite (1.5-2% deviation). In the system for which we have the most robust constraints, CO₂-calcite, there is excellent agreement between our calculations and experimental data over a broad range of temperatures (0-900 °C). Similarly, there is good to excellent correspondence between calculation and experiment for most other low to moderate atomic mass carbonate minerals (aragonite to strontianite). The agreement is not as good for high atomic mass carbonates (witherite, cerussite, otavite). In the case of witherite and cerussite, the discrepancy may be due, in part, to our calculation methodology, which does not account for the effect of cation mass on the magnitude of vibrational frequency shifts associated with heavy isotope substitution. However, the calculations also reveal an incompatibility between the high- and low-temperature experimental datasets for witherite and cerussite. Specifically, the shapes of fractionation factor versus 1/T² curves in the calcite-witherite and calcite-cerussite systems do not conform to the robust constraints on the basic shape of these curves provided by theory. This suggests that either the high- or low-temperature datasets for both minerals is in error. Dolomite-calcite fractionation factors derived from our calculations fall within the wide range of fractionations for this system given by previous experimental and natural sample studies. However, our compilation of available low-temperature (25-80 °C) experimental data reveal an unusual temperature dependence of fractionations in this system; namely, the data indicate an increase in the magnitude of fractionations between dolomite (or proto-dolomite) and calcite with increasing temperature. Such a trend is incompatible with theory, which stipulates that fractionations between carbonate minerals must decrease monotonically with increasing temperature. We propose that the anomalous temperature dependence seen in the low-temperature experimental data reflect changes in the crystallinity and degree of cation ordering of the dolomite phase over this temperature interval and the effect these changes have on the vibrational frequencies of dolomite. Similar effects may be present in natural systems at low-temperature and must be considered in applying experimental or theoretical fractionation data to these systems. In nearly all cases, carbonate mineral-calcite fractionation factors given by the present calculations are in as good or better agreement with experimental data than are fractionations derived from semi-empirical bond strength methods.     

华北克拉通几个地区古元古代碳酸盐岩地层C-O同位素特征

对华北克拉通古元古代辽河群、中条群和湾子群的碳酸盐岩进行了C、O同位素研究。辽河群王家沟组条带状大理岩的δ13CPDB变化于-1.02‰~3.14‰之间,大部分在0.16‰~1.79‰之间,平均值为1.07‰,稍高于海相碳酸盐岩的δ13C平均值0.5‰,δ18OPDB变化于-17.2‰~-10.1‰之间,大部分在-13.4‰~-10.1‰之间,20组数据的均值为-11.9‰。中条群余家山组大理岩的δ13CPDB变化于-0.2‰~0.8‰之间,大部分在0~0.3‰之间,前14个样品的δ13C平均值为0.34‰,稍低于海相碳酸盐岩的δ13C平均值,后16个样品的δ13C平均值为0.54‰,与海相碳酸盐岩的δ13C平均值基本一致,其δ18OPDB变化于-7.9‰~-6.1‰之间,大部分在-7.3‰~-6.1‰之间,前14个样品的δ18O平均值为-6.80‰,后16个样品的δ18O平均值为-6.68‰,两个剖面上的δ18O值没有明显差别。阜平宋家口南湾子群大理岩δ13CPDB变化于1.0‰~3.8‰之间,平均值为2.65‰,明显高于海相碳酸盐岩的δ13C平均值0.5‰,其δ18OPDB变化于-8.8‰~-5.7‰之间,平均值为-6.97‰。研究结果表明所研究的大理岩均形成于一个比较稳定而又相对波动的气候环境,大理岩沉积期间存在海平面和气温旋回变化但没有突变事件。湾子群宋家口剖面大理岩对Jatulian事件有响应,中条群余家山组大理岩对Jatulian事件没有响应,辽河群王家沟组是否存在对Jatulian事件响应还不确切。     

Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher ^34S and lower sulfur content, but that in the south of China has lower ^34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.     

水溶液中溶质的扩散同位素分馏研究

稳定同位素分析是判定水溶液中溶质的组成、来源、迁移和转化过程与规律的重要工具,在自由扩散等物理化学作用下,对溶质的同位素分馏研究是稳定同位素技术应用的重要基础.本研究介绍了溶质的扩散过程与其同位素分馏效应之间的联系,论述了研究溶质扩散过程中引入的稳定同位素分馏现象的意义,描述了水溶液中溶质扩散的不同模拟实验方法及相关研...     

贵州龙动物群产出层位碳氧同位素研究

贵州龙动物群是二叠-三叠纪大绝灭后海洋生态系统辐射发展阶段最晚期的典型代表,为了解其古环境信息,对贵州省兴义地区顶效及周边产地开展了精细剖面测量,采集碳酸盐岩进行了全岩碳氧同位素测试。测试结果显示：泥麦谷剖面δ¹³C值分布范围-6.3‰~2.6‰,δ¹⁸O分布范围在-5.7‰~-1.2‰;谢米剖面δ¹³C值分布范围在-4.5‰~2.5‰,δ¹⁸O在-5.7‰~-1.2‰;坝尾剖面δ¹³C值分布范围在0.5‰~2‰,δ¹⁸O在-6.4‰~0.1‰;顶效剖面δ¹³C值分布范围在-4.3‰~2.1‰,δ¹⁸O在-7.3‰~-2.5‰。根据碳氧同位素数据相关性分析显示泥麦谷、谢米、坝尾剖面的同位素值受后期成岩作用影响较小。在泥麦谷、谢米及顶效贵州龙动物群产出层位下段均出现明显的δ¹³C负异常,与低水位时期海洋生物快速死亡密切相关,也与火山作用存在一定的联系。由于顶效剖面受后期成岩作用影响,笔者利用泥麦谷、谢米及坝尾剖面δ¹⁸O数据对兴义地区古海水温度进行了恢复,结果显示温度分布在19~27℃,平均为23℃左右,说明当时属于温暖气候环境。     

含Cu硫化物中S、Fe同位素分馏系数的第一性原理计算

Cu在自然界主要以硫化物的形式存在,目前只确定了几种含Cu硫化物的S同位素分馏系数以及黄铜矿的Fe同位素分馏系数,而且不同研究者确定的系数有很大的差别,使得S、Fe同位素在研究铜矿床的形成、演化等方面不能很好地发挥示踪作用。因此,本文基于第一性原理计算确定了0~1 000℃温度范围内主要含Cu硫化物的S同位素简约配分函数比（10³lnβ_34-32）,以及Cu-Fe硫化物的Fe同位素简约配分函数比（10³lnβ_57-54）。重S同位素在这些含Cu硫化物中的富集顺序为铜蓝>方黄铜矿>黄铜矿≈黑硫铜镍矿>斑铜矿>辉铜矿,重Fe同位素在Cu-Fe硫化物中的富集顺序为方黄铜矿≈黄铜矿>低温斑铜矿>高温斑铜矿>中温斑铜矿>Cu₈Fe₄S₈（中温斑铜矿的可能变体）。含Cu硫化物的10³lnβ_34-32与S原子的配位数、金属-S平均键长、S原子形成的所有化学键的平均键长没有明显的相关性,而Cu-Fe硫化物的10³lnβ_57-54与Fe—S平均键长基本成线性负相关关系。辉铜矿相变引起的S同位素分馏特别大,而斑铜矿相变时产生的S同位素分馏却可以忽略不计。本文的计算结果将会为探讨斑岩铜矿及其它类型的硫化物矿床的成因提供支持。     

水-岩反应过程中的锂硼同位素分馏变化规律

作为热液体系中成矿的一个重要前提,水-岩反应一直以来都是矿床学的重要研究内容,亦是国际地学界的前沿问题。该过程伴随着同位素的交换,使流体和岩石的同位素组成发生变化。硼和锂同位素作为非传统的稳定同位素示踪工具,常用于限定流体和岩石的热液反应过程。本文对水-岩反应过程中影响硼和锂同位素分馏的因素作了较全面概述,包括温度、pH值、溶解过程、表面交换反应以及次生矿物的沉淀过程,并取得了一些主要认识:(1)一般地,低温或者高pH值时流体更快速富集11B并且在反应结束时有更高的δ11B值;低温(150℃)时锂进入次生矿物中,高温(200℃)时锂从岩石中萃取出来。(2)初始物质的溶解过程与表面交换反应对锂同位的分馏几乎没有影响。(3)一般而言,次生矿物的形成使7Li优先丢失进入溶液而富集重同位素。最后简单陈述了水-岩反应过程中硼和锂同位素组成的质量平衡模拟计算以及反映流体和岩石的同位素组成的变化。     

针铁矿-四方纤铁矿-水体系氧同位素分馏的实验研究

针铁矿是非常重要的三价铁氧化物之一,其氧同位素组成对于古环境再造具有很大的价值。以4种不同的铁化合物作为Fe3+离子的源物质,于30～120℃范围内,采用强迫水解方法,在不同同位素组成的水中分别实验合成针铁矿和四方纤铁矿。结果表明,以Fe(NO3)3·9H2O、NH4Fe(SO4)2·12H2O、Fe(SO4)3·7H2O为Fe3+源物质合成的是纯针铁矿,而以FeCl3·6H2O为Fe3+源物质合成的是四方纤铁矿。氧同位素分析显示,在30～120℃范围内实验测定的针铁矿-水体系和四方纤铁矿-水体系氧同位素分馏几乎不可区分,并且满足下列分馏关系:103lnα针铁矿-水=9.59×103/T-26.39103lnα四方纤铁矿-水=8.85×103/T-24.44实验测定的针铁矿-水体系氧同位素分馏不仅与前人实验结果一致,而且与增量方法理论计算相近。由于实验采用不同反应途径得到了一致的分馏结果,因此所测定的针铁矿-水体系氧同位素分馏代表了热力学平衡。     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.     

Biological fractionation of Zn isotopes in aquatic invertebrates

Recent advances in analytical instrumentation have made it more feasible to measure isotope ratios of many elements. In particular, modem multicollector-inductively coupled plasma mass spectrometers can measure isotope ratios of many elements with extremely high precision. As a consequence, we can begin to explore biological fractionation in a systematic way and hence develop isotope ratio measurements as a tool to explore the environmental geochemistry of trace metals. In this presentation we will discuss the problems and potential of measuring isotope ratios of zinc in biological samples from systems with non-specific contamination. This will include such issues as the importance of matrix removal to the measurement of valid isotope ratios, mass bias correction and the availability of standard reference materials. Recent data on isotope ratios of Zn in the aquatic invertebrate Mysis relicta will be presented. These animals are of particular interest because they changed their feeding pattern from juveniles to adults. Thus they can be used to test the hypothesis that differences in the isotopic signature of food sources may determine receptor signatures. The data indicate that there are significant differences in signatures at the different life stages. However, the continual uptake and loss of metals over an organism＇s life span may also lead to fractionation.