矿物流体包裹体中稀有气体的保存能力初探

查明流体包裹体中稀有气体的保存能力,对于判断其初始组分特征是否因后生作用而发生改变具有重要意义.文章以Ar为例,从扩散动力学角度对稀有气体地球化学研究中常用的矿物中流体包裹体稀有气体的保存能力进行了定量分析和系统比较,计算了Ar在这些矿物中的封闭温度以及不同温度条件下的保存时间,得出相同条件下各矿物对Ar、He等保存能...     

Noble gas components in planetary atmospheres and interiors in relation to solar wind and meteorites

We discuss observed xenon isotopic signatures in solar system reservoirs and possible relationships. The predominant trapped xenon component in ordinary chondrites (OC) is OC-Xe and its isotopic signature differs from Xe in ureilites, in carbonaceous chondrites, in the atmospheres of Earth and Mars, and in the solar wind. Additional minor Xe components were identified in type 3 chondrites and in the metal phase of chondrites. The OC-Xe and ureilite signatures are both consistent with varying mixtures of HL-Xe and slightly mass fractionated solar-type Xe. Xenon in the Martian atmosphere is found to be strongly mass fractionated by 37.7‰ per amu, relative to solar Xe, favoring the heavy isotopes. Xenon in SNC’s from the Martian mantle show admixture of solar-type Xe, which belongs to an elementally strongly fractionated component. The origin of the isotopic signatures of Ne and Xe in the terrestrial atmosphere are discussed in the light of evidence that the Xe isotopic fractionations in the Martian and terrestrial atmospheres are consistent. However, in the terrestrial atmospheric Xe component excesses are observed for¹³²Xe and also for^129,131Xe, relative to fractionated solar Xe. The suggested chemically fractionated fission Xe component (CFF-Xe) seems to closely match the above excesses. We discuss models of origin for planetary volatiles and possible processes driving their evolution to present day compositions.     

Laser microprobe for the study of noble gases and nitrogen in single grains: A case study of individual chondrules from the Dhajala meteorite

A laser microprobe capable of analysing nitrogen and noble gases in individual grains with masses less than a milligram is described. It can be used in both continuous wave (CW) mode, useful for stepwise heating of an individual grain, as well as in pulsed mode, useful for ablating material from a small selected area of a sample, for gas extraction. We could achieve low blanks (in ccSTP units) for 4He(4.8 x 10{-12}),²²Ne(1.0 x 10{-12}),³⁶Ar(1.0 x10 ^-13),⁸⁴Kr(2.9 x 10{-14}),¹³² Xe(2.6 x 10{-14}), and N (87 pg), using this system. Preliminary data for individual chondrules from the Dhajala meteorite show that noble gases and nitrogen from grains as small as 170 microgram can be analysed using the present laser microprobe setup. The amount of trapped neon in Dhajala chondrules is very small, and nitrogen in the chondrules is isotopically heavier as compared to the bulk meteorite.     

Solubilities of noble gases in magnetite: implications for planetary gases in meteorites

Solubilities of noble gases in magnetite were determined by growing magnetite in a noble-gas atmosphere between 450 and 700°K. Henry's law is obeyed at pressures up to 10^?2 atm for He, Ne, Ar and up to 10^?5 atm for Kr, Xe, with the following distribution coefficients at 500° (cc STP g^?1 atm^?5): He 0.042, Ne 0.016, Ar 3.6, Kr 1.3, Xe 0.88, some 10²–10⁵ times higher than previous determinations on silicate and fluoride melts. Apparent heats of solution in kcal/mole are: He ?2.42 ±0.12, Ne ?2.20 ±0.10, Ar ?15.25 ±0.25, Kr ?13.0 ±0.3, Xe ?12-5 ± 0.5. These values, too, stand in sharp contrast with earlier determinations on melts which were small and positive, but are comparable to the values for clathrates. Presumably the gases are held in anion vacancies.Extrapolation of the magnetite data to the formation temperature of C1 chondrites, 360°K, shows that the Ar_p³⁶ content of Orgueil magnetite could be acquired by equilibrium solubility at a total nebular pressure of 4 × 10^?6 atm. In the absence of data for silicates (the principal host phase of planetary gas), an attempt is made to estimate the solubilities required to account for planetary gases in meteorites. These values do not appear grossly unreasonable in the light of the magnetite data, when structural differences between the two minerals are taken into account. It seems that equilibrium solubility may be able to account for four features of planetary gas: elemental ratios, amounts, correlations with other volatiles and retentive siting. It cannot account for the isotopic fractionation of planetary gas, however.     

Noble gases,nitrogen and cosmic ray exposure age of the Sulagiri chondrite

The Sulagiri meteorite fell in India on 12 September 2008,LL6 chondrite class is the largest among all the Indian meteorites.Isotopic compositions of noble gases(He,Ne,Ar,Kr and Xe) and nitrogen in the Sulagiri meteorite and cosmic ray exposure history are discussed.Low cosmogenic(~(22)Ne/~(21)Ne)_c ratio is consistent with irradiation in a large body.Cosmogenic noble gases indicate that Sulagiri has a 4πcosmic-ray exposure(CRE) age of 27.9 ± 3.4 Ma and is a member of the peak of CRE age distribution of IX chondrites.Radiogenic ~4He and ~(40)Ar concentrations in Sulagiri yields the radiogenic ages as 2.29 and4.56 Ca,indicating the loss of He from the meteorite.Xenon and krypton are mixture of Q and spallogenic components.     

Reconstruction of climatic change quantitatively with dissolved noble gases in groundwaters

One kind of climatic proxies only can describes the comparative change of temperature or rainfall, but dissolved noble gases in groundwater can be used to date groundwater, calculate temperature and rainfall, and this method can give the exact change value of three parameters in one time. Dissolved noble gases in groundwater has four sources, radioactivity-formed noble gases which are from radioactive decay of some radioactive elements in the aquifers, balance-dissolved noble gases from dissolved air in balance condition in the course of supplying, excess noble gases from excess air for groundwater-air mixing and water table changing during infiltrating, and outer-interfused noble gases from outer interfusing air in open conditions during runoff. Because the contents of radioagenic noble gases in groundwater are correlated to flowing time, such as He, the age of groundwater can be dated with 4He based on the solubility of He and the radioactive intensity of aquifers. The solubility of noble gases is the function of temperature. We can compare the contents of balance-dissolved noble gases in groundwater with the temperature-solubility experimental curves of noble gases, and calculate the forming temperature of groundwater. The contents of excess noble gases are related to the water column of infiltration which can reveal the volume of rainfall in a given period of time in general, and it may increase along with the pressure of aquifers when groundwater table rises greatly. So we can calculate the value of rainfall by comparing the contents of excess noble gases in groundwater samples with those in modem groundwater. Reconstruction of climatic change on a quantitative basis with the method of dissolved noble gases in Hebei plain （China） shows that the temperature changed from 3.8 to 19.7℃ in the past forty thousand years, it decreased to 3.8℃ in 16000 a B.P. but higher than 19.7℃ in 5060 a B.P. The rainfall was about 600mm during 40000 to 15000 a B.P., then decreased gradually to 410mm in 11000 a B.P., but subsequently increased to 950mm in 4400 a B.P. The change of noble gas temperature is consistent with 180 shift, and 6D varied with the change of other climatic proxy, such as rainfall.     

微量陨石激光熔样稀有气体测定方法

微量陨石激光熔样稀有气体测定方法是一种可以在微米尺度上对几毫克陨石样品进行准确稀有气体同位素分析的方法,克服了传统全岩熔融法在测量时存在样品用量大、前处理过程复杂和样品稀有气体分布不均导致不同组分的宇宙射线暴露历史无法进一步区分等问题。但是由于该方法所用样品体积小和样品用量低,要求实验室具有超低本底的稀有气体提取系统,目前国内在微量陨石稀有气体分析技术方面尚处于起步阶段。本文采用金刚石激光样品窗成功研制了超低本底的气体提取系统,通过系统体积标定和天平称量误差、热本底、干扰元素、质量歧视及质谱灵敏度等参数的校正,在中国科学院地质与地球物理研究所建立了微量陨石激光熔样稀有气体测定方法,并对毫克级微量钙长辉长无球粒陨石Millbillillie粉末标样进行了稀有气体同位素含量和比值测定,计算获得准确一致的宇宙暴露年龄。该方法的建立,将为我国迅速发展的比较行星学和深空探测提供重要技术支撑。     

测定地下水补给温度与降雨量的最新方法--惰性气体法

地下水补给温度与降雨量是重要的水文地质参数,已有的测定方法大多只能给出其相对变化.本文介绍的惰性气体法能同时求得地下水补给温度与降雨量的值,其基本原理是:利用地下水中惰性气体的平衡溶解量计算出地下水补给温度;在得到地下水补给温度的基础上,利用地下水中惰性气体的"过剩空气"量计算出降雨量.该方法主要适用于封闭条件下的深层地下水.     

Isotopic anomalies of noble gases in meteorites and their origins—III. LL-chondrites

Nine LL-chondrites were studied by a selective etching technique, to characterize the noblegas components in three mineral fractions: HF-HCl-solubles (silicates, metal, troilite, etc.; comprising ～ 99% of the meteorite), chromite and carbon (～ 0.3–0.7%) and Q (a poorly characterized mineral defined by its solubility in HNO₃, comprising ～ 0.05% of the meteorite but containing most of the Ar, Kr, Xe and a neon component of ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{= 10.9 ± 0.8}$). The ${}^{20}\text{Ne}{}^{36}\text{Ar}$ ratio in Q falls wi petrologic type and rising ³⁶Ar content, as expected for condensation from a cooling solar nebula, but contrary to the trend expected for metamorphic losses. Chondrites of different petrologic types therefore cannot all be derived from the same volatile-rich ancestor, but must have formed over a range of temperatures, with correspondingly different intrinsic volatile contents.The CCFXe (carbonaceous chondrite fission) component varies systematically with petrologic type. The most primitive LL3s (Krymka, Bishunpur, Chainpur) contain substantial amounts of CCFXe in chromite-carbon, enriched relative to primordial Xe as shown by high ${}^{136}\text{Xe}{}^{132}\text{Xe}$ (0.359–0.459, vs 0.310 for primordial Xe). These are accompanied by He and by Ne with ${}^{20}\text{Ne}{}^{22}\text{Ne}\text{≈ 8.0}$ and by variable amounts of a xenon component enriched in the light isotopes. The chromite in these meteorites is compositionally peculiar, containing substantial amounts of Fe(III). These meteorites, as well as Parnallee (LL3) and Hamlet (LL4) also contain CCFXe in phase Q, heavily diluted by primordial $\text{Xe}\text{(}{}^{136}\text{Xe}{}^{132}\text{Xe}\text{= 0.317–0.329)}$. On the other hand, LL5s and 6s (Olivenza, St. Séverin, Manbhoom and Dhurmsala) contain no CCFXe in either mineral. This deficiency must be intrinsic rather than caused by metamorphic loss, because Q in these meteorites still contains substantial amounts of primordial Ne.If CCFXe comes from a supernova, then its distribution in LL-chondrites requires three presolar carrier minerals of the right solubility properties, containing three different xenon components in certain combinations. These minerals must be appropriately distributed over the petrologic types, together with locally produced Q containing primordial gases, and they must be isotopically normal, in contrast to the gases they contain. On the other hand, if CCFXe comes from fission of a volatile superheavy element, then its decrease from LL3 to LL6 can be attributed to progressively less complete condensation from the solar nebula. Ad hoc assumptions must of the host phase Q, its association with ferrichromite and the origin of the associated xenon component enriched in the light isotopes.Soluble minerals in LL3s and LL4s contain a previously unobserved, solar xenon component, which, however, is not derived from the solar wind. Three types of ‘primordial’ xenon thus occur side-by-side in different minerals of the same meteorite: strongly fractionated Xe in ferrichromite and carbon, lightly fractionated Xe in phase Q, and ‘solar’ Xe in solubles. Because the first two can apparently be derived from the third by mass fractionation, it seems likely that all were trapped from the same solar nebula reservoir, but with different degrees of mass fractionation.     

Presolar grains from meteorites: Remnants from the early times of the solar system

This review provides an introduction to presolar grains - preserved stardust from the interstellar molecular cloud from which our solar system formed - found in primitive meteorites. We describe the search for the presolar components, the currently known presolar mineral populations, and the chemical and isotopic characteristics of the grains and dust-forming stars to identify the grains’ most probable stellar sources.     

Noble gases reveal the complex groundwater mixing pattern and origin of salinization in the Azraq Oasis,Jordan

Azraq Oasis in the eastern Jordanian desert is an important freshwater resource of the country. Shallow groundwater reserves are heavily exploited since the 1980s and in consequence the groundwater table dropped significantly. Furthermore, some wells of the major well field drilled into the shallow aquifer show an increasing mineralization over the past 20 years. A previous study using conventional tracers did not result in a satisfactory explanation, from where the salt originates and why only a few wells are affected. In this study, the application of dissolved noble gases in combination with other tracer methods reveals a complex mixing pattern leading to the very localized salinization within the well field. It is found that primarily the wells affected by salinization 1) contain distinctly more radiogenic ⁴He than the other wells, indicating higher groundwater age, and 2) exhibit ³He/⁴He ratios that argue for an imprint of deep fluids from the Earth's mantle.However, the saline middle aquifer below is virtually free of mantle helium, which infers an upstream from an even deeper source through a nearby conductive fault. The local restriction of the salinization process is explained by the wide range of permeabilities of the involved geologic units. As the wells abstract water from the whole depth profile, they initially pump water mainly from the well conductive top rock layer. As the groundwater table dropped, this layer fell progressively dry and, depending on the local conductivity profile, some wells began to incorporate more water from the deeper part of the shallow aquifer into the discharge. These are the wells affected by salinization, because according to the presented scheme the deep part of the shallow aquifer is enriched in both salt and mantle fluids.     

五大连池和宽甸地幔包体的惰性气体同位素特征——MORB型地幔和交代型地幔

黑龙江五大连池科洛和辽宁宽甸的碱性玄武岩中地幔包体的惰性气体同位素的地球化学特征研究表明,东北地区表现了地幔的不均匀性。五大连池地区的地幔包体中的^3He／^4He比为4．5～5．3RA,明显低于MORB的值,具有被交代的大陆富集地幔特征。氩同位素^40Ar/^36Ar比的变化在557～4005。结合玄武岩和地幔包体的矿物学特征和微量元素地球化学特征,显示五大连池地区的岩浆源区可能遭受过来自壳源物质或和古俯冲事件有关的富H2O—CO2流体的交代作用。辽宁宽甸黄椅山的样品^3He／^4He比为7．30～7.52RA,氩同位素^40Ar/^36Ar比的范围在1496～7677。宽甸黄椅山地区的则显示了具亏损地幔MORB的特点,反映了未经地壳组分改造的大陆地幔的特征。本文通过对两种不同类型的地幔岩的研究,认为东北地区大陆地幔存在MORB型亏损地幔和交代型地幔两种类型,反映了各自不同的演化机理。     

The origin of iron silicides in ureilite meteorites

Ureilite meteorites contain iron silicide minerals including suessite (Fe,Ni)₃Si, hapkeite (Fe₂Si) and xifengite (Fe₅Si₃). Despite occurring mostly in brecciated varieties presumed to be derived from the regolith of the ureilite parent asteroid, suessite has also been confirmed in one lithology of a dimict ureilite (NWA 1241). In contrast, Si-bearing Fe-metals occur in both brecciated and unbrecciated ureilites, implying that they were formed throughout the ureilite parent asteroid. We examined major, minor and trace element data of Fe-metals in seven brecciated ureilites (DaG 319, DaG 999, DaG 1000, DaG 1023, DaG 1047, EET 83309, and EET 87720) in addition to the dimict ureilite NWA 1241.In this study we show that the silicides and Si-bearing metals in ureilites have similar siderophile trace element patterns; therefore, the precursors to the silicides were indigenous to the ureilite parent body. Si-free kamacite grains in brecciated ureilites show flatter, more chondritic siderophile element patterns. They may also be derived from the interior of the ureilite parent body, but some may be of exogenous origin (impactor debris), as are rare taenite grains.On Earth, iron silicides are often formed under high-temperature and strongly reducing conditions (e.g. blast furnaces, lightning strikes). On the Moon, hapkeite (Fe₂Si) and other silicides have been found in the regolith where they were formed by impact-induced space weathering. In the Stardust aerogel, iron silicides derived from comet Wild2 were also formed by an impact-related reduction process. Silicides in ureilite regolith breccias may have formed by similar processes but ureilites additionally contain abundant elemental carbon which probably acted as a reducing agent, thus larger and more abundant silicide grains were formed than in the lunar regolith or cometary material. The origin of suessite in NWA 1241 may be analogous to that of reduced lithologies in the terrestrial mantle, although a regolith origin may also be possible since this sample is shown here to be a dimict breccia.     

西太平洋海底海山富钴结壳惰性气体同位素组成及其来源

采用高真空气体质谱系统测定了西太平洋麦哲伦海山富钴结壳不同层圈及其基岩的惰性气体丰度和同位素组成,结果显示:(1)西太平洋富钴结壳主要是水成成因,其中惰性气体来源不同,He 绝大多数来自宇宙尘(IDPs),少量来自陆源风成微粒;Ar 主要来自海水溶解的大气,少量来自陆源风成微粒或沉积岩建造水;Ne 和 Xe 主要来自海水中溶解大气, 少量来自宇宙尘;(2)在具三层结构的结壳中,亮煤层(致密层)的惰性气体同位素相对外层和疏松层有较大的不同,显示大洋磷酸岩化对早期沉积的结壳惰性气体组成有较大的影响,如导致~4He 的升高和~3He/~4He 的显著降低;(3)太平洋富钴结壳玄武岩基岩的~3He/~4He 非常低,为0.0095～0.074Ra,与本区磷块岩基岩(0.087Ra)相似,而远低于正常海底玄武岩的~3He/~4He 比值,显示这些基岩曾与富含放射性成因~4He 和 P 的上升洋流或沉积物中建造水发生过水/岩反应,这个过程将释放出较多的成矿元素,有利于富钴结壳的形成,海底海山玄武岩中较低的 He 同位素组成可作为富钴结壳的找矿标志之一。     

Noble gases dissolved in groundwater in a volcanic aquifer: Helium isotopes in the Kumamoto Plain

This study Investigates a tracing method using dissolved noble gases to survey the groundwater flow in a large groundwater basin. The tracing method is based on measuring the concentrations of noble gases and the ratio of helium isotopes in groundwater samples. Since it is very difficult to detect trace amounts of noble gases and helium with high accuracy in a 15-ml groundwater sample, dissolved gases were extracted and purified, then a high-resolution mass spectrometer was used for measurement and comparison with standard samples. We used this method with samples from a confined aquifer formed by the deposition of pyroclastic flow in the Kumamoto Plain on the west side of Mt. Aso in central Kyushu, Japan. The groundwater basin under the plain is divided into four small basins, based on the helium concentrations and isotope ratios, with two major groundwater flows. One flow is buried by the Aso pyroclastic flow along the old Kase River; the other is along the Tsuboi River Valley. These two groundwater flows were identified from the different helium isotope-ratios. The helium component from the deep mantle is mixed into the groundwater under the Kumamoto Plain. Finally, data on the concentrations and ratios of³He to⁴He in groundwater samples were used to determine the location of faults in the volcanic aquifer.     

赣南地热气体起源的同位素与地球化学证据

对取自赣南地区10个温泉的地热气体进行了气体化学成分及氦、碳、氖同位素组成的分析。该区地热气体可分为CO₂型和N₂型两种类型。CO₂型地热气体分布在赣南东南部地区,主要成分是CO₂,占总体积96.47%以上,二氧化碳气体的δ¹³C值为 -5.50‰～-3.49‰（PDB）,平均为 -4.66‰,为幔源无机成因,其氦同位素组成为1.36～2.27 R_a,具有明显的幔源成因特征,最高约有28.2%的氦源于地幔,其N₂-Ar-He关系研究表明,该型地热气体中的氮源于地幔-地壳-大气混合成因。研究揭示该区CO₂型地热气体属幔源无机成因气,是地幔脱气作用的产物。N₂型地热气体分布在赣南西部地区,N₂含量占91.04%以上,其中二氧化碳气体的δ¹³C值为 -23.7‰～-12.6‰,平均为 -17.82‰,为壳源有机成因,其氦同位素组成为0.06～0.13 R_a,具有明显的壳源放射性成因特征,³He/⁴He 与 ⁴He/²⁰Ne关系和He-Ar-N₂关系研究表明,N₂型温泉气主要来源于大气,并有壳源气体的贡献。     

Isotopic anomalies of noble gases in meteorites and their origins—VII. C3V carbonaceous chondrites

Noble gases were measured in bulk samples of the C3V chondrites Grosnaja, Vigarano, and Leoville, and in HF,HCl-insoluble residues before and after etching with HNO₃. The residues were characterized by INAA and SEM. Gas components were determined, directly or by subtraction, for the following fractions: HF,HCl-solubles (?98% of the meteorite), ‘sphase Q’, a poorly characterized trace mineral that is insoluble in HCl-HF but soluble in HNO₃, and an insoluble residue, consisting of ferrichromite, carbonaceous matter, and spinel.Bulk meteorites show some correlation of the noble-gas pattern with McSween's subclasses: two ‘oxidized’ C3V's—Allende (LEWIS et al, 1975) and Grosnaja— have lower Ar/Xe but higher Ne/Xe ratios than the ‘reduced’ C3V's—Vigarano and Leoville—which are transitional to LL3's and C3O chondrites in both respects. An HCl-soluble mineral of high Ar/Xr ratio seems to be responsible. In other respects, the 3 C3V's of this study resemble Allende, with only moderate differences. Phase Q contains most of the Ar, Kr, Xe, but only small amounts of Ne; the etched residues contain planetary Ne ($\text{Ne}{}^{20}\text{Ne}{}^{22}\text{? 8.5}$) and the controversial CCFXe component, enriched in the heavy Xe isotopes ($\text{Xe136}\text{Xe132 ? 0.4–0.5}$). The CCFXe is accompanied by an ‘L-Xe’ component that is enriched in the light Xe isotopes. The proportion of the two is virtually constant in C3V's. as in all other C-chondrites. in contrast to the ~ 2-fold variation in ordinary chondrites.C3V's have systematically higher $\text{Xe}{}^{136}\text{Xe}{}^{132}$ ratios, and hence higher ratios of CCFXe to planetary Xe, than do other chondrite classes. This may reflect some peculiarity in their formation conditions, favoring uptake of CCFXe.     

Sorption of noble gases by solids,with reference to meteorites. II. Chromite and carbon

We studied trapping of noble-gases by chromite and carbon: two putative carriers of primordial noble gases in meteorites. Nineteen samples were synthesized in a Ne-Ar-Kr-Xe atmosphere at 440 K to 720 K, by the following reactions: Fe,Cr + 4H₂O → (Fe,Cr)₃O₄ + 4H₂ (1) or Fe,Cr + 4CO → (Fe,Cr)₃O₄ + 4C + carbides (2)The reactant metal films were prepared either by vacuum evaporation of alloy or by thermal decomposition of Fe- and Cr-carbonyls. The products—including Fe₃O₄, Cr₂O₃, carbides, and unreacted metal—were partially separated by selective solvents, such as HCl, H₂SO₄?H₃PO₄, or HClO₄. Samples were characterized by XRD, SEM, and atomic absorption; noble gases were measured by mass spectrometry. Surface areas, as measured by the BET method, were 2 to 100 m²/g.All samples are dominated by an adsorbed noble gas component that is largely released upon heating at ?400°C or slight etching. Elemental abundance patterns show that this component is derived from the highest-pressure noble gas reservoir seen by the sample—atmosphere or synthesis vessel—indicating that desorption or exchange rates at room T are slow on the time scale of our experiments (up to 1 year). Adsorptive capacity is reduced by up to 2 orders of magnitude upon light etching with HClO₄ (though the surface area actually doubles in this treatment) and, less drastically, by heating. Apparently some active adsorption sites are destroyed by these treatments. A trapped component (typically 30% of the total) is readily detectable only in samples synthesized at partial pressures close to or greater than atmospheric.Noble gas contents roughly obey Henry's Law, but show only slight, if any, correlations with composition, surface area, or adsorption temperature. (Geometric) mean distribution coefficients for bulk samples and HCl-residues are, in 10^?3 cc STP/g atm: Xe (100), Kr (15), Ar (3.5), Ne (0.62). Elemental fractionations are large and variable, but are essentially similar for the adsorbed and trapped components, or for chromite and carbon. They bracket the values for the corresponding meteoritic minerals.

     

19.

Sorption of noble gases by solids,with reference to meteorites. I. Magnetite and carbon     

Jongmann Yang  Roy S. Lewis  Edward Anders 《Geochimica et cosmochimica acta》1982,46(6):841-860

To simulate trapping of meteoritic noble gases by solids, 18 samples of Fe₃O₄ were synthesized in a noble gas atmosphere at 350–720 K by the reactions: 3Fe + 4H₂O → Fe₃O₄ + 4H₂ (Ne, Ar, Kr, Xe) 3Fe + 4CO → Fe₃O₃ + 4C + carbides (Xe only) Phases were separated by selective solvents (HgCl₂, HCl). Noble gas contents were analyzed by mass spectrometry, or, in runs where 36 d Xe¹²⁷ tracer was used, by γ-counting. Surface areas, as measured by the BET method, ranged from 1 to 400 m²/g. Isotopic fractionations were below the detection limit of 0.5%/m.u.Sorption of Xe on Fe₃O₄ and C obeys Henry's Law between $\text{1 × 10}{}^{\mathrm{?8}}$ and $\text{4 × 10}{}^{\mathrm{?5}}$ atm, but shows only a slight temperature dependence between 650 and 720 K ($\text{ΔH}{}_{\mathrm{sol}}\text{= ?4 ± 2}\text{kcal/mole}$). The mean distribution coefficient K_Xe is $\text{0.28 ± 0.09}$ cc STP/g atm for Fe₃O₄ and only a factor of $\text{1.2 ± 0.4}$ greater for C; such similarity for two cogenetic phases was predicted by Lewis et al. (1977). Stepped heating and etching experiments show that 20–50% of the total Xe is physically adsorbed and about 20% is trapped in the solid. The rest is chemisorbed with $\text{ΔH}{}_{\mathrm{s}}\text{? ?13}\text{kcal/mole}$. The desorption or exchange half-time for the last two components is >10² yr at room temperature.Etching experiments showed a possible analogy to “Phase $\text{Q}$” in meteorites. A typical carbon + carbide sample, when etched with HNO₃, lost 47% of its Xe but only 0.9% of its mass, corresponding to a ~0.6 Å layer. Though this etchable, surficial gas component was more thermolabile than $\text{Q}$ (release $\text{T}$ below 1000°C, compared to 1200–1600°C), another experiment shows that the proportion of chemisorbed Xe increases upon moderate heating (1 hr at 450°C). Apparently adsorbed gases can become “fixed” to the crystal, by processes not involving volume diffusion (recrystallization, chemical reaction, migration to traps, etc.). Such mechanisms may have acted in the solar nebula, to strengthen the binding of adsorbed gases.Adsorbed atmospheric noble gases are present in all samples, and dominate whenever the noble gas partial pressure in the atmosphere is greater than that in the synthesis. Many of the results of Lancet and Anders (1973) seem to have been dominated by such an atmospheric component; others are suspect for other reasons, whereas still others seem reliable. When the doubtful samples of Lancet and Anders are eliminated or corrected, the fractionation pattern—as in our samples—no longer peaks at Ar, but rises monotonically from Ne to Xe. No clear evidence remains for the strong temperature dependence claimed by these authors.     

20.

含油气盆地油气同位素地球化学研究概述   总被引：18，自引：7，他引：18  

徐永昌  刘文汇等 《沉积学报》2001,19(2):161-168

以气体地球化学国家重点实验室工作为主，简要概述了对我国含油气的同位素地球化学研究。1．烃气的同位素地球化学：讨论了天然气成因新模式与气藏烃气同位素组成的关系，低演化阶段天然气同位素分馏的二阶段模式，云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2．稀有气体同位素地球化学：阐述了^3He/^4He值与中国构造分区，幔源氮的复合成藏和幔源甲烷问题以及气源对比等。3．液态烃同位素地球化学：简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。     

	$\text{Ne}\text{Xe}$	$\text{Ar}\text{Xe}$	$\text{Kr}\text{Xe}$
Geom. mean	0.006	0.035	0.15
Range	0.0004-0.03	0.01-0.2	0.06-0.4

Sorption of noble gases by solids,with reference to meteorites. I. Magnetite and carbon

To simulate trapping of meteoritic noble gases by solids, 18 samples of Fe₃O₄ were synthesized in a noble gas atmosphere at 350–720 K by the reactions: 3Fe + 4H₂O → Fe₃O₄ + 4H₂ (Ne, Ar, Kr, Xe) 3Fe + 4CO → Fe₃O₃ + 4C + carbides (Xe only) Phases were separated by selective solvents (HgCl₂, HCl). Noble gas contents were analyzed by mass spectrometry, or, in runs where 36 d Xe¹²⁷ tracer was used, by γ-counting. Surface areas, as measured by the BET method, ranged from 1 to 400 m²/g. Isotopic fractionations were below the detection limit of 0.5%/m.u.Sorption of Xe on Fe₃O₄ and C obeys Henry's Law between $\text{1 × 10}{}^{\mathrm{?8}}$ and $\text{4 × 10}{}^{\mathrm{?5}}$ atm, but shows only a slight temperature dependence between 650 and 720 K ($\text{ΔH}{}_{\mathrm{sol}}\text{= ?4 ± 2}\text{kcal/mole}$). The mean distribution coefficient K_Xe is $\text{0.28 ± 0.09}$ cc STP/g atm for Fe₃O₄ and only a factor of $\text{1.2 ± 0.4}$ greater for C; such similarity for two cogenetic phases was predicted by Lewis et al. (1977). Stepped heating and etching experiments show that 20–50% of the total Xe is physically adsorbed and about 20% is trapped in the solid. The rest is chemisorbed with $\text{ΔH}{}_{\mathrm{s}}\text{? ?13}\text{kcal/mole}$. The desorption or exchange half-time for the last two components is >10² yr at room temperature.Etching experiments showed a possible analogy to “Phase $\text{Q}$” in meteorites. A typical carbon + carbide sample, when etched with HNO₃, lost 47% of its Xe but only 0.9% of its mass, corresponding to a ~0.6 Å layer. Though this etchable, surficial gas component was more thermolabile than $\text{Q}$ (release $\text{T}$ below 1000°C, compared to 1200–1600°C), another experiment shows that the proportion of chemisorbed Xe increases upon moderate heating (1 hr at 450°C). Apparently adsorbed gases can become “fixed” to the crystal, by processes not involving volume diffusion (recrystallization, chemical reaction, migration to traps, etc.). Such mechanisms may have acted in the solar nebula, to strengthen the binding of adsorbed gases.Adsorbed atmospheric noble gases are present in all samples, and dominate whenever the noble gas partial pressure in the atmosphere is greater than that in the synthesis. Many of the results of Lancet and Anders (1973) seem to have been dominated by such an atmospheric component; others are suspect for other reasons, whereas still others seem reliable. When the doubtful samples of Lancet and Anders are eliminated or corrected, the fractionation pattern—as in our samples—no longer peaks at Ar, but rises monotonically from Ne to Xe. No clear evidence remains for the strong temperature dependence claimed by these authors.     

含油气盆地油气同位素地球化学研究概述

以气体地球化学国家重点实验室工作为主，简要概述了对我国含油气的同位素地球化学研究。1．烃气的同位素地球化学：讨论了天然气成因新模式与气藏烃气同位素组成的关系，低演化阶段天然气同位素分馏的二阶段模式，云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2．稀有气体同位素地球化学：阐述了^3He/^4He值与中国构造分区，幔源氮的复合成藏和幔源甲烷问题以及气源对比等。3．液态烃同位素地球化学：简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。