惰性气体同位素确定地热流体循环深度

地热系统惰性气体同位素地球化学是地热成因研究的重要手段。许多惰性气体同位素都可用于地热系统的研究中,主要目的为揭示热田的热源性质、深-浅层地热流体的内在联系和循环深度等。本文从惰性气体理化特点、样品采集、测试技术及数据等若干方面介绍了惰性气体研究方法,重点探讨了在自由气和溶解气两种形态下,热泉、喷气孔、热水井不同环境下的惰性气体采样方法,还介绍了成熟的惰性气体同位素的测试方法,即利用磁偏转静态真空质谱计分析测试方法,最后基于世界各地典型地热系统的惰性气体测试数据,讨论地热系统的气体来源判别,不同气源的混合比例计算等,进而确定地热流体循环深度。     

Noble gases in ultramafic xenoliths from San Carlos,Arizona

This work reports the results of noble gas (Ne, Ar, Kr, Xe) analyses of accidental mantle xenoliths from San Carlos, Arizona. Except for the addition of radiogenic ⁴⁰Ar and mass fractionation effects, the isotopic structures of these gases are indistinguishable from atmospheric composition. The absence of ¹²⁹Xe excesses in these rocks may reflect indirect mixing of atmospheric gases with the source region of the xenoliths. The dominant influence on the noble gas abundances in the San Carlos xenoliths appears to have been diffusive gas loss, which may have occurred in a mantle metamorphic event or during contact with the host basanite magma. Evidence is presented for the partitioning of significant amounts of the heavy noble gases into fluid inclusions in the xenolith minerals; the proportion of each gas in the inclusions increases with increasing atomic weight of the gas, possibly reflecting solubility effects. The noble gases are present in greater concentration in pyroxenes than in olivine, similar to the behavior of other incompatible elements.     

新疆准噶尔地区金矿床成矿流体稀土元素地球化学特征

新疆准噶尔地区出现大量不同类型金矿床，为了探讨它们的成因，为金矿床的找矿勘探提供依据。笔者进行了哈图、包谷图、阔尔真阔腊、科克萨依等金矿床包裹体流体中稀土元素及同位素等研究。结果表明，尽管它们成矿形式不同，规模不等，但它们的金均主要来自深源，并有地层物质参与。其中哈图金矿石英脉型矿体与蚀变岩型矿体是两种不同来源的流体叠加成矿，石英脉型矿体主要与哈图岩体岩浆流体关系密切，蚀变岩型矿体与深源流体有关。包谷图、阔尔真阔腊金矿矿、科克萨依金矿成矿流体主要来源于深源，成矿过程中受到浅成流体的综合影响。矿物包裹体流体的稀土元素特征主要反映了原始成矿流体来源，矿物的稀土元素特征可能较多地体现了矿床特有的后期地质作用，这在今后研究中将进一步探讨。     

中国天然气中稀有气体丰度和同位素组成

中国天然气中稀有气体丰度和同位素组成徐胜（中国科学院兰州地质研究所，兰州７３００００）关键词中国天然气、稀有气体丰度和同位素、稀有气体来源稀有气体在地质作用过程中的丰度和同位素组成变化几乎不受复杂化学反应的影响，而主要取决于溶解、吸附、吸着和核反应等...     

Relations of noble gas abundances to petrogenesis and magmatic evolution of some oceanic basalts and related differentiated volcanic rocks

We report the results of noble gas analyses (Ne, Ar, Kr, and Xe) of a transitional basalt from the East Pacific Rise; a mantle xenolith, alkali basalt and trachyte from Guadalupe Island; and a basalt and icelandite from Isla Tortuga. The results for the East Pacific Rise basalt and comparison with the noble gas compositions of glassy mid-ocean ridge tholeiites indicate that the heavy noble gas patterns of these basalts can be accounted for by mixing of a juvenile reservoir with an atmosphere-related reservoir. This mixing may take place during hydration of the glassy basalts. Comparison of the noble gas compositions of these submarine basalts with those of the subaerial oceanic extrusives studied suggests that subaerial extrusives may provide noble gas samples which are less contaminated with air gases than do submarine extrusives. Our results for Guadalupe and Tortuga basalts and their differentiates provide evidence for the exsolution and loss of a gas (fluid) phase accompanying or subsequent to fractional crystallization at shallow depths. The gas loss probably took place prior to extrusion and was apparently rapid, since it did not fractionate the heavy noble gases.     

稀有气体同位素地球化学研究的某些进展

稀有气体的化学惰性使其在示踪成矿流体方面具有明显的优越性,其与碳、氢、氧、硫、锶、钕、铅同位素方法,以及卤素方法等结合使用,不但可以避免单一方法的片面性,还可以相互补充,相互印证,更好地示踪成矿流体的来源与演化,进而探讨矿床的成矿机制。本文归纳了近年来稀有气体同位素与其他同位素体系联合应用的研究进展,及其存在的问题和发展趋势。     

鄂尔多斯盆地苏里格大气田天然气成藏地球化学研究

苏里格大气田位于鄂尔多斯盆地伊陕斜坡西北部,属于典型的低渗砂岩气田。对天然气组分和同位素组成研究表明,苏里格大气田上古生界天然气以干气为主、湿气为辅,甲烷含量为82.729%~98.407%,干燥系数为84.7%~98.8%,δ¹³C₁值为-36‰~-30‰,δ¹³C₂值为-26‰~-21‰,属于高成熟度的煤成气;气田范围内各井区天然气组分和碳同位素组成变化较小,暗示其来源和成藏过程的一致性。根据储层流体包裹体镜下观察、包裹体均一温度、含烃包裹体丰度、颗粒荧光定量(QGF)、包裹体激光拉曼分析,苏里格大气田上古生界储层发育盐水包裹体、气体包裹体、液态烃包裹体、CO₂包裹体等不同类型流体包裹体,主要产于石英次生加大边、微裂隙及胶结物中;包裹体均一温度分布呈连续的单峰态,分布范围为80~180℃,主峰温度为100~145℃;上古生界砂岩储层样品的含烃包裹体丰度不高(多为1%~5%),QGF强度较低(1~10pc)。研究认为,苏里格大气田天然气充注可能是一个连续的过程,主要经历了一期成藏,其主要成藏期为晚侏罗世-早白垩世。通过生气动力学与碳同位素动力学的研究表明,苏里格大气田天然气主要来源于苏里格地区及周缘的石炭-二叠系煤系烃源岩,为近源充注、累积聚气成藏。     

Upwelling of Mantle-derived Material in Southeast China: Evidence from Noble Gas Isotopes

Shallow groundwater collected in Chaozhou,Huizhou,and Guangzhou allowed testing of concentrations and the isotope ratios of noble gases.Based on the calculated noble gas temperature(NGT)and the ratio of noble gas isotopes,the recharge temperature,recharge source,and residence time of groundwater can be calculated.In addition,the contribution of noble gas components from different sources to the sample components can be assessed.In the Huizhou area,according to the 1/Xe vs.Ne/Xe and NGT data,the shallow sandstone-confined water samples in the Shiba area and the unconfined water samples of the Huangshadong are in different temperature ranges,indicating that they have different recharge sources,both in time or space.The He components in the samples are calculated to obtain the content of radiogenic ⁴He in the crust and to simulate the groundwater ages.The noble gas isotope ratios show the addition of mantle components into the basalt aquifers and sandstone aquifers in Chaozhou and Huizhou.Except for atmospheric and crustal sources,there is a certain proportion of mantle-derived components in the shallow underground cold water in Huizhou and Chaozhou.The noble gases in the Chaozhou groundwater have an obvious mantle signature,allowing speculation that there is a deep fluid carrying mantle characteristics.This upwelling of mantle-derived material might be caused by the India-Eurasia collision or that between the Philippine Sea Plate and the Eurasian Plate.     

天然气的混合类型及其判识

通过对天然气独特的物理、化学特征研究,探讨了不同成因来源天然气混合的机理和条件,将天然气混合划分为有机来源与无机来源的混合、有机质不同母质形成天然气的混合和不同成熟阶段有机成因气混合等三大类型。通过具体实例解剖研究了天然气混合的判识,初步建立了不同成因类型天然气的混合的模式。     

稀有气体同位素地球化学在矿床学研究中的应用进展

稀有气体因其化学惰性以及在不同来源地质体中的同位素组成差异很大,在研究成矿流体来源、演化和壳-幔相互作用过程中具有非常重要的意义。另外,由于~4He、⁴⁰Ar是放射成因子体同位素,具有年代积累效应,因此,它们常被用于同位素测年。本文简要回顾了流体包裹体中稀有气体同位素的后生影响和样品、分析方法选择注意事项,以及近年来稀有气体同位素在成矿流体示踪,⁴⁰K-⁴⁰Ar、⁴⁰Ar-39Ar定年及(U-Th)/He定年方面的研究进展。已有研究证实流体包裹体中的稀有气体可能受后期扩散丢失、后生叠加和同位素分馏的影响,要根据目的选择不同的分析方法;稀有气体同位素可以示踪不同类型矿床的流体来源、演化及壳-幔相互作用、稀有气体同位素与卤素联合运用可以用来指示流体和盐度来源、演化过程以及矿物沉淀机制等,~3He/热的研究可以追溯流体的热源及其运移方式;流体包裹体⁴⁰Ar-³⁹Ar可以用于矿床直接定年,表生含钾矿物的⁴⁰K-⁴⁰Ar、⁴⁰Ar-³⁹Ar定年以及锆石、磷灰石和铁氧化物(U-Th)/He定年可为矿床及氧化带的形成时间、矿床形成后的抬升、剥露历史、古气候演化等重大地质问题讨论提供大量有意义的信息。     

惰性气体同位素和卤素示踪成矿流体来源

本文简要地回顾了流体包裹体中He、Ar同位素以及Cl、Br和I在现代地壳流体和古成矿流体示踪研究方面的应用，认为利用流体包裹体中He、Ar同位素和Cl、Br、I可以有效地示踪地幔流体参与成矿的过程及其背景，有助于深入研究流体的热场和运移轨迹。     

稀有气体同位素地球化学应用前景

稀有气体有4个源区,包括大气、地下水、地壳和地幔;其中地幔稀有气体又可分为上地幔和下地幔2个源区。不同源区的稀有气体在同位素组成上截然不同,因而可以利用稀有气体同位素进行有关地质和地球化学过程的示踪。稀有气体同位素组成不仅对查明成矿流体的性质和来源及矿床成因具有重要作用,而且还可以为正确理解大规模成矿作用的地球动力学背景和全面弄清大型一超大型矿集区的时空分布规律提供重要线索。     

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 gases in the unique Kaidun meteorite

Two examined fragments of the Kaidun meteorite principally differ in the concentrations of isotopes of noble gases and are very heterogeneous in terms of the isotopic composition of the gases. Because these fragments belong to two basically different types of meteoritic material (EL and CR chondrites), these characteristics of noble gases could be caused by differences in the cosmochemical histories of the fragments before their incorporation into the parent asteroid. As follows from the escape kinetics of all gases, atoms of trapped and cosmogenic noble gases are contained mostly in the structures of two carrier minerals in the samples. The concentrations and proportions of the concentrations of various primary noble gases in the examined fragments of Kaidun are obviously unusual compared to data on most currently known EL and CR meteorites. In contrast to EL and CR meteorites, which contain the primary component of mostly solar provenance, the elemental ratios and isotopic composition of Ne and He in the fragments of Kaidun correspond to those typical of the primary components of A and Q planetary gases. This testifies to the unique conditions under which the bulk of the noble gases were trapped from the early protoplanetary nebula. The apparent cosmic-ray age of both of the Kaidun fragments calculated based on cosmogenic isotopes from ³He to ¹²⁶Xe varies from 0.027 to 246 Ma as a result of the escape of much cosmogenic isotopes at relatively low temperatures. The extrapolated cosmic-ray age of the Kaidun meteorite, calculated from the concentrations of cosmogenic isotopes of noble gases, is as old as a few billion years, which suggests that the material of the Kaidun meteorite could be irradiated for billions of years when residing in an unusual parent body.     

Planetary and pre-solar noble gases in meteorites

Noble gases are not rare in the Universe, but they are rare in rocks. As a consequence, it has been possible to identify in detailed analyses a variety of components whose existence is barely visible in other elements: radiogenic and cosmogenic gases produced in situ, as well as a variety of “trapped” components – both of solar (solar wind) origin and the “planetary” noble gases. The latter are most abundant in the most primitive chondritic meteorites and are distinct in elemental and isotopic abundance patterns from planetary noble gases sensu strictu, e.g., those in the atmospheres of Earth and Mars, having in common only the strong relative depletion of light relative to heavy elements when compared to the solar abundance pattern. In themselves, the “planetary” noble gases in meteorites constitute again a complex mixture of components including such hosted by pre-solar stardust grains.The pre-solar components bear witness of the processes of nucleosynthesis in stars. In particular, krypton and xenon isotopes in pre-solar silicon carbide and graphite grains keep a record of physical conditions of the slow-neutron capture process (s-process) in asymptotic giant branch (AGB) stars. The more abundant Kr and Xe in the nanodiamonds, on the other hand, show a more enigmatic pattern, which, however, may be related to variants of the other two processes of heavy element nucleosynthesis, the rapid neutron capture process (r-process) and the p-process producing the proton-rich isotopes.“Q-type” noble gases of probably “local” origin dominate the inventory of the heavy noble gases (Ar, Kr, Xe). They are hosted by “phase Q”, a still ill-characterized carbonaceous phase that is concentrated in the acid-insoluble residue left after digestion of the main meteorite minerals in HF and HCl acids. While negligible in planetary-gas-rich primitive meteorites, the fraction carried by “solubles” becomes more important in chondrites of higher petrologic type. While apparently isotopically similar to Q gas, the elemental abundances are somewhat less fractionated relative to the solar pattern, and they deserve further study. Similar “planetary” gases occur in high abundance in the ureilite achondrites, while small amounts of Q-type noble gases may be present in some other achondrites. A “subsolar” component, possibly a mixture of Q and solar noble gases, is found in enstatite chondrites. While no definite mechanism has been identified for the introduction of the planetary noble gases into their meteoritic host phases, there are strong indications that ion implantation has played a major role.The planetary noble gases are concentrated in the meteorite matrix. Ca-Al-rich inclusions (CAIs) are largely planetary-gas-free, however, some trapped gases have been found in chondrules. Micrometeorites (MMs) and interplanetary dust particles (IDPs) often contain abundant solar wind He and Ne, but they are challenging objects for the analysis of the heavier noble gases that are characteristic for the planetary component. The few existing data for Xe point to a Q-like isotopic composition. Isotopically Q-Kr and Q-Xe show a mass dependent fractionation relative to solar wind, with small radiogenic/nuclear additions. They may be closer to “bulk solar” Kr and Xe than Kr and Xe in the solar wind, but for a firm conclusion it is necessary to gain a better understanding of mass fractionation during solar wind acceleration.     

Variations in the composition and origin of hydrocarbon gases from inclusions in minerals of the Khibiny and Lovozero plutons,Kola Peninsula,Russia

Relationships between methane and its homologues mainly contained in fluid microinclusions have been studied in 332 monomineralic fractions from the Khibiny and Lovozero alkaline plutons. Hydrocarbon gases (HCG) were extracted for subsequent chromatographic analysis using the bulk method of sample comminution. The molecular weight distribution (MWD) of gaseous alkanes in the same and associated minerals is different depending on geological setting of the samples. The molecular mass of HCG increases (i) with decrease in temperature and capture of fluid inclusions in the course of transformation of primary magmatic minerals and the formation of late minerals as products of intensified postmagmatic processes; (ii) in the direction from khibinite at the margin and foyaite in the core of the Khibiny pluton to the central ring structure; and (iii) from the bottom to top of the differentiated complex in the Lovozero pluton. The results obtained coupled with other geochemical data suggest multistage generation and transformation of hydrocarbons from the magmatic to the final low-temperature hydrothermal stage. The MWD of hydrocarbon components in gases occluded by minerals can serve as an indicator of conditions characteristic of rock and ore formation, as well as of the consecutive formation and transformation of associated minerals revealing ambiguous and controversial relationships.     

Noble gas distribution in oceanic basalt glasses

The distribution of noble gases has been investigated in six MORB glass samples using stepwise heating, vacuum crushing and the analysis of grain size fractions. These experiments indicate a strong noble gas partitioning into CO₂-filled vesicles. An inhomogeneous distribution of argon isotopes within individual glasses is observed in several cases and is believed to result from the combined effects of the deep-seated component partitioning into vesicles and the contamination of the residual component dissolved in the glass by atmospheric noble gases. Using a mixing diagram, we are able to discriminate against atmospheric contamination and estimate the Ar partition coefficients. These coefficients are in qualitative agreement with the Henry's law constant for silicate melts.     

Source identification of methane in groundwater in shale gas development areas: A critical review of the state of the art,prospects, and future challenges

Shale gas exploration and development carry the risk of causing groundwater contamination and enhancing the greenhouse effect through methane leakage. Identifying the source of abnormal methane in groundwater of shale gas development areas is becoming a research hotspot in the fields of groundwater and climate change. This paper reviews the traditional methodology in identifying sources of methane and its deficiency in groundwater application. Then potential and advantages of using noble gases were discussed on how to overcome these limitations of the traditional method. Finally, based on noble gas, the current application status and future challenges of methane source identification in groundwater were analyzed. It can be summarized as:(1) due to chemical and/or microbial processes in the aquifer system, the traditional methodology for methane source identification, which utilizes molecular and isotopic compositions of hydrocarbon gas, has multiple interpretationsand large uncertainties;(2) the non-reactive nature and well-characterized isotopic compositions of noble gases in the atmosphere, hydrosphere, and crust, make noble gases ideal indicators of the sources of methane in groundwater. Moreover, the mechanism of formation and release of crustal noble gas prevent shale gas signatures from being interfered with by natural gas;(3) the key scientific tasks surrounding the use of noble gases for methane source identification include quantitatively separating the components of atmosphere-derived, mantle-derived, and crust-derived noble gases from the bulk noble gases in groundwater. It quantifies the solubility fractionation of noble gases induced by water-gas interaction during methane migration to the aquifer. The application of noble gases can bring a new perspective to tracing the source of methane in groundwater and is of great significance to the protection of groundwater quality in shale gas development areas and mitigation of climate change.     

Noble gas evidence for two fluids in the Baca (Valles Caldera) geothermal reservoir

Noble gas elemental and isotopic abundances were measured in steam from four wells in the Baca geothermal reservoir located in the Valles Caldera, New Mexico. The ${}^{40}\text{Ar}{}^{36}\text{Ar}$ ratio and noble gas elemental abundances relative to ³⁶Ar are all strongly correlated with 1/³⁶Ar, the inverse of the argon content. Ratios of (α,n)-produced ²¹Ne1 and radiogenic ⁴⁰Ar1 to total ⁴He (dominantly radiogenic) are nearly constant at 2.1 × 10?8 and 0.20, respectively. The ${}^3\text{He}{}^4\text{He}$ ratio covers a restricted range of 3.9 to 4.8 times atmospheric. The high ³He content of the gas indicates the presence of a helium component ultimately derived from the mantle. Kr and Xe isotopic compositions are close to atmospheric; excess ¹²⁹Xe1 is <0.25% of the total ¹²⁹Xe.The high degree of linear correlation among the various noble gas results strongly suggests that the Baca reservoir contains two distinct fluids that are produced in varying proportions from individual wells. The noble gases in fluid A (~2900 mg/1 C1) are air-like, but with lighter gases and isotopes preferentially enriched. The fluid A ³⁶Ar content is low, only 13% that of 10°C air-saturated water (ASW). The second fluid, B (~ 1700 mg/1 C1), is the dominant carrier of the radiogenic and mantle-derived gases. The heavier non-radiogenic gases are preferentially enriched in fluid B, and its ³⁶Ar content is very low, only 5–7% ASW. The source of the noble gases in fluid A is tentatively ascribed to leaching of the relatively young (<1.4 m.y.) volcanic Bandelier Tuff. The radiogenic gases and mantle-derived helium in fluid B suggest a deeper source, possibly including gases escaping from a magma.     

Field experiments yield new insights into gas exchange and excess air formation in natural porous media

Gas exchange between seepage water and soil air within the unsaturated and quasi-saturated zones is fundamentally different from gas exchange between water and gas across a free boundary layer, e.g., in lakes or rivers. In addition to the atmospheric equilibrium fraction, most groundwater samples contain an excess of dissolved atmospheric gases which is called “excess air”. Excess air in groundwater is not only of crucial importance for the interpretation of gaseous environmental tracer data, but also for other aspects of groundwater hydrology, e.g., for oxygen availability in bio-remediation and in connection with changes in transport dynamics caused by the presence of entrapped air bubbles. Whereas atmospheric solubility equilibrium is controlled mainly by local soil temperature, the excess air component is characterized by the (hydrostatic) pressure acting on entrapped air bubbles within the quasi-saturated zone. Here we present the results of preliminary field experiments in which we investigated gas exchange and excess air formation in natural porous media. The experimental data suggest that the formation of excess air depends significantly on soil properties and on infiltration mechanisms. Excess air was produced by the partial dissolution of entrapped air bubbles during a sprinkling experiment in fine-grained sediments, whereas similar experiments conducted in coarse sand and gravel did not lead to the formation of excess air in the infiltrating water. Furthermore, the experiments revealed that the noble gas temperatures determined from noble gases dissolved in seepage water at different depths are identical to the corresponding in situ soil temperatures. This finding is important for all applications of noble gases as a paleotemperature indicator in groundwater since these applications are always based on the assumption that the noble gas temperature is identical to the (past) soil temperature.