An approach to noble-gas isotopic compositions in natural gases and gas-source tracing in the Ordos Basin, China

Isotopic compositions of noble gases, i.e. He Ar Kr and Xe, are measured in natural gases from the Zhongbu gasfield in the Ordos Basin. And heavy noble-gas isotopes (Kr, Xe) are here first used in geochemically studying natural gases and gas-source correlation. Isotopic compositions of heavy noble gases in natural gases, especially Xe, show two-source mixing in the Zhongbu gasfield. Gas sources are somewhat different in the northeast and the southwest of the gasfield. Generally, the gas source of the Lower Paleozoic makes a greater contribution in the southwest than in the northeast in the field. Two kinds of gases can be differentiated from isotopic compositions of heavy noble gases and from their relation with the Ar isotopic composition, Therefore, the comprehensive study on isotopic compositions of light and heavy noble gases can supply more useful information on gas-source correlation and tracing.     

Seawater subduction controls the heavy noble gas composition of the mantle

The relationship between solar volatiles and those now in the Earth's atmosphere and mantle reservoirs provides insight into the processes controlling the acquisition of volatiles during planetary accretion and their subsequent evolution. Whereas the light noble gases (helium and neon) in the Earth's mantle preserve a solar-like isotopic composition, heavy noble gases (argon, krypton and xenon) have an isotopic composition very similar to that of the modern atmosphere, with radiogenic and (in the case of xenon) solar contributions. Mantle noble gases in a magmatic CO2 natural gas field have been previously corrected for shallow atmosphere/groundwater and crustal additions. Here we analyse new data from this field and show that the elemental composition of non-radiogenic heavy noble gases in the mantle is remarkably similar to that of sea water. We challenge the popular concept of a noble gas 'subduction barrier'--the convecting mantle noble gas isotopic and elemental composition is explained by subduction of sediment and seawater-dominated pore fluids. This accounts for approximately 100% of the non-radiogenic argon and krypton and 80% of the xenon. Approximately 50% of the convecting mantle water concentration can then be explained by this mechanism. Enhanced recycling of subducted material to the mantle plume source region then accounts for the lower ratio of radiogenic to non-radiogenic heavy noble gas isotopes and higher water content of plume-derived basalts.     

Noble gas isotopic compositions of deep carbonate rocks from the Tarim Basin

Abundances and isotopic compositions of noble gases (He, Ne, Ar, Kr) with various existence states in carbonate rocks from the Tacan1 Well have been investigated by means of the stepwise heating technique. The elemental abundance patterns of noble gases in the samples show the enrichment of heavy noble gases and depletion of ²⁰Ne relative to the atmosphere, which are designated as type-Ⅰand are similar to that observed in water, natural gases and sedimentary rocks. The ³He/⁴He ratios of deep carbonate samples at lower and medium temperature (300—700℃) and a majority of samples at higher temperature (1100—1500℃) steps are very similar to those of natural gases in the same strata in this area, this feature of radiogenic crustal helium shows that the Tazhong Uplift is relatively stable. However, significant helium and argon isotopic anomalies are found at the 1100℃ step in the Middle-Upper Ordovician carbonate rock, suggesting the incorporation of mantle-derived volatiles, this may be due to minor igneous minerals contained in sedimentary carbonate rocks. The ⁴⁰Ar/ ³⁶Ar ratios in the Cambrian carbonate rock are slightly higher than those in Ordovician carbonate rocks, which may reflect the influence of the chronologic accumulation effect of crust radiogenic ⁴⁰Ar. Argon isotopes of various existence states in source rocks are much more different, both ³⁸Ar/ ³⁶Ar and ⁴⁰Ar/ ³⁶Ar ratios at the higher temperature steps are higher than those at the lower temperature steps.     

The 'zero charge' partitioning behaviour of noble gases during mantle melting

Noble-gas geochemistry is an important tool for understanding planetary processes from accretion to mantle dynamics and atmospheric formation. Central to much of the modelling of such processes is the crystal-melt partitioning of noble gases during mantle melting, magma ascent and near-surface degassing. Geochemists have traditionally considered the 'inert' noble gases to be extremely incompatible elements, with almost 100 per cent extraction efficiency from the solid phase during melting processes. Previously published experimental data on partitioning between crystalline silicates and melts has, however, suggested that noble gases approach compatible behaviour, and a significant proportion should therefore remain in the mantle during melt extraction. Here we present experimental data to show that noble gases are more incompatible than previously demonstrated, but not necessarily to the extent assumed or required by geochemical models. Independent atomistic computer simulations indicate that noble gases can be considered as species of 'zero charge' incorporated at crystal lattice sites. Together with the lattice strain model, this provides a theoretical framework with which to model noble-gas geochemistry as a function of residual mantle mineralogy.     

A stable argon compound

The noble gases have a particularly stable electronic configuration, comprising fully filled s and p valence orbitals. This makes these elements relatively non-reactive, and they exist at room temperature as monatomic gases. Pauling predicted in 1933 that the heavier noble gases, whose valence electrons are screened by core electrons and thus less strongly bound, could form stable molecules. This prediction was verified in 1962 by the preparation of xenon hexafluoroplatinate, XePtF6, the first compound to contain a noble-gas atom. Since then, a range of different compounds containing radon, xenon and krypton have been theoretically anticipated and prepared. Although the lighter noble gases neon, helium and argon are also expected to be reactive under suitable conditions, they remain the last three long-lived elements of the periodic table for which no stable compound is known. Here we report that the photolysis of hydrogen fluoride in a solid argon matrix leads to the formation of argon fluorohydride (HArF), which we have identified by probing the shift in the position of vibrational bands on isotopic substitution using infrared spectroscopy. Extensive ab initio calculations indicate that HArF is intrinsically stable, owing to significant ionic and covalent contributions to its bonding, thus confirming computational predictions that argon should form a stable hydride species with properties similar to those of the analogous xenon and krypton compounds reported before.     

Extreme oxygen isotope ratios in the early Solar System

The origins of the building blocks of the Solar System can be studied using the isotopic composition of early planetary and meteoritic material. Oxygen isotopes in planetary materials show variations at the per cent level that are not related to the mass of the isotopes; rather, they result from the mixture of components having different nucleosynthetic or chemical origins. Isotopic variations reaching orders of magnitude in minute meteoritic grains are usually attributed to stellar nucleosynthesis before the birth of the Solar System, whereby different grains were contributed by different stars. Here we report the discovery of abundant silica-rich grains embedded in meteoritic organic matter, having the most extreme 18O/16O and 17O/16O ratios observed (both approximately 10(-1)) together with a solar silicon isotopic composition. Both O and Si isotopes indicate a single nucleosynthetic process. These compositions can be accounted for by one of two processes: a single exotic evolved star seeding the young Solar System, or irradiation of the circumsolar gas by high energy particles accelerated during an active phase of the young Sun. We favour the latter interpretation, because the observed compositions are usually not expected from nucleosynthetic processes in evolved stars, whereas they are predicted by the selective trapping of irradiation products.     

Fast delivery of meteorites to Earth after a major asteroid collision

Very large collisions in the asteroid belt could lead temporarily to a substantial increase in the rate of impacts of meteorites on Earth. Orbital simulations predict that fragments from such events may arrive considerably faster than the typical transit times of meteorites falling today, because in some large impacts part of the debris is transferred directly into a resonant orbit with Jupiter. Such an efficient meteorite delivery track, however, has not been verified. Here we report high-sensitivity measurements of noble gases produced by cosmic rays in chromite grains from a unique suite of fossil meteorites preserved in approximately 480 million year old sediments. The transfer times deduced from the noble gases are as short as approximately 10(5) years, and they increase with stratigraphic height in agreement with the estimated duration of sedimentation. These data provide powerful evidence that this unusual meteorite occurrence was the result of a long-lasting rain of meteorites following the destruction of an asteroid, and show that at least one strong resonance in the main asteroid belt can deliver material into the inner Solar System within the short timescales suggested by dynamical models.     

Noble gases in corundum megacrysts from the basalts in Changle, Shandong Province, eastern China

This study presents noble gaseous data of the corundum megacrysts from the Cenozoic basalts in Changle, Shandong Province, eastern China. It is known that no noble gaseous data of corundum megacryst have been documented before. The 3He/4He ratios (1.13-7.37 Ra) of the corundums from Changle vary from atmosphere to MORB values; the 20Ne/22Ne (9.67-10.75) and 21Ne/22Ne (0.0280-0.0372) data define two linear trends on Ne three-isotope diagram, respectively, along the MFL and the correlation line between atmosphere and MORB; the 38Ar/36Ar (0.177-0.194) ratios, the 40Ar/36Ar (280.9 -404.2) ratios and the 128-136Xe/132Xe ration with obvious 129Xe excess are generally higher than at-mospheric component, but the 40Ar/36Ar ratios are much closer to atomospheric ratio. The isotopic compositions of noble gases (particularly for He and Ar) of the corundums are similar to those of py-roxene, anorthoclase megacrysts, and mantle-derived xenoliths from this area, and those of man-tle-derived xenoliths from several areas in eastern China. Therefore, the noble gases trapped in the corundums probably are from mantle source, representing a ‘mixed fluid' produced by the interaction between the lithospheric mantle and fluids releasing from the convective plate. Both the noble gas isotopic compositions and the oxygen isotopic compositions of the solid corundums are not the characteristics of crustal source. These suggest that the corundums crystallized from mantle-derived magmas with minimal crustal contamination.     

Oxygen isotopic compositions of zircons from pyroxenite of Daoshichong,Dabieshan: Implications for crust-mantle interaction

Oxygen isotopic compositions of zircons from pyroxenite (～145 Ma) of Daoshichong, Dabieshan have been measured by an ion microprobe. Both within the single grain and among different grains, oxygen isotopic ratios are homogeneous, δ 18O = (7.66‰±0.46)‰ (1 SD, 1 σ = 0.10, n = 22). High δ 18O values indicate that the mantle-derived parent magma of Daoshichong pyroxenite have undergone interaction with crustal materials. Combing with other geochemical constraints, the way of crust-mantle interaction is suggested to be source mixing other than crustal contamination. The time interval between crust-mantle interaction and formation of the parent magma of Daoshichong pyroxenite is less than several million years. The crustal component involving in crust-mantle interaction is mafic lower crust, and the parent magma of pyroxenite possibly contain large proportion (>37%) of such lower crust.     

Possible cometary origin of heavy noble gases in the atmospheres of Venus, Earth and Mars

Models that trace the origin of noble gases in the atmospheres of the terrestrial planets (Venus, Earth and Mars) to the 'planetary component' in chondritic meteorites confront several problems. The 'missing' xenon in the atmospheres of Mars and Earth is one of the most obvious; this gas is not hidden or trapped in surface materials. On Venus, the absolute abundances of neon and argon per gram of rock are higher even than those in carbonaceous chondrites, whereas the relative abundances of argon and krypton are closer to solar than to chondritic values (there is only an upper limit on xenon). Pepin has developed a model that emphasizes hydrodynamic escape of early, massive hydrogen atmospheres to explain the abundances and isotope ratios of noble gases on all three planets. We have previously suggested that the unusual abundances of heavy noble gases on Venus might be explained by the impact of a low-temperature comet. Further consideration of the probable history of the martian atmosphere, the noble-gas data from the (Mars-derived) SNC meteorites and laboratory experiments on the trapping of noble gases in ice lead us to propose here that the noble gases in the atmospheres of all of the terrestrial planets are dominated by a mixture of an internal component and contribution from impacting icy planetesimals (comets). If true, this hypothesis illustrates the importance of impacts in determining the volatile inventories of these planets.     

Palaeotemperature reconstruction from noble gases in ground water taking into account equilibration with entrapped air

Noble-gas concentrations in ground water have been used as a proxy for past air temperatures, but the accuracy of this approach has been limited by the existence of a temperature-independent component of the noble gases in ground water, termed 'excess air' whose origin and composition is poorly understood. In particular, the evidence from noble gases in a Brazilian aquifer for a cooling of more than 5 C in tropical America during the Last Glacial Maximum has been called into question. Here we propose a model for dissolved gases in ground water, which describes the formation of excess air by equilibration of ground water with entrapped air in quasi-saturated soils. Our model predicts previously unexplained noble-gas data sets, including the concentration of atmospheric helium, and yields consistent results for the non-atmospheric helium isotopes that are used for dating ground water. Using this model of excess air, we re-evaluate the use of noble gases from ground water for reconstructing past temperatures. Our results corroborate the inferred cooling in Brazil during the Last Glacial Maximum, and indicate that even larger cooling took place at mid-latitudes.     

Stardust silicates from primitive meteorites

Primitive chondritic meteorites contain material (presolar grains), at the level of a few parts per million, that predates the formation of our Solar System. Astronomical observations and the chemical composition of the Sun both suggest that silicates must have been the dominant solids in the protoplanetary disk from which the planets of the Solar System formed, but no presolar silicates have been identified in chondrites. Here we report the in situ discovery of presolar silicate grains 0.1-1 microm in size in the matrices of two primitive carbonaceous chondrites. These grains are highly enriched in 17O (delta17O(SMOW) > 100-400 per thousand ), but have solar silicon isotopic compositions within analytical uncertainties, suggesting an origin in an oxygen-rich red giant or an asymptotic giant branch star. The estimated abundance of these presolar silicates (3-30 parts per million) is higher than reported for other types of presolar grains in meteorites, consistent with their ubiquity in the early Solar System, but is about two orders of magnitude lower than their abundance in anhydrous interplanetary dust particles. This result is best explained by the destruction of silicates during high-temperature processing in the solar nebula.     

Anomalously high δ D and micro-scale hydrogen isotope heterogeneities in the mantle: Ion microprobe analysis of am-iboles from peridotite xenoliths at Nushan, eastern China

Hydrogen isotopic compositions of four amphibole grains from three pieces of lherzolite xenoliths in Cenozoic basanites of Nushan, eastern China have been analyzed by ion microprobe. δ D values of all analyzed points range from ?94‰ to +46‰, some of which are much higher than the highest δ D (+8‰) reported previously for mantle materials. The heterogeneities of D/H ratios within single grains have been observed, the variation of δ D is up to 80‰ on the scale of less than 400 ?m. No correlation between hydrogen isotopic ratios and hydrogen contents can be found, implying that the scatter of δ D values could not result from a late shallow process such as hydrogen loss or hydrothermal alterations and should be considered as inherited from the source at depth. Chemical compositions of Nushan amphiboles are very homogeneous, excluding the fact that the scatter of δ D values could arise from variable fractionation factors between a single fluid source and minerals. Therefore, metasomatic fluids responsible for the formation of Nushan amphiboles should be heterogeneous and result in the observed large variable and anomalously high δ D values of amphiboles. We suggested that such metasomatic fluids could be related to magma degassing in the mantle source. Based on the D-H diffusion data and the scale of hydrogen isotope heterogeneities, it was inferred that the mantle metasomatism took place soon before the eruption of host magma.     

Diverse supernova sources of pre-solar material inferred from molybdenum isotopes in meteorites

Variations in the isotopic composition of some components in primitive meteorites demonstrate that the pre-solar material was not completely homogenized, nor was it processed at sufficiently high temperatures to erase the signatures of the diverse stellar sources. This is in accord with the observation that accretion disks of young stellar objects are at relatively low temperatures. Carbonaceous chondrites are considered to represent the 'average' Solar System composition; the rare pre-solar grains in the matrixes of carbonaceous chondrites have been used to identify some sources of the pre-solar material. Here we report that the molybdenum isotopic composition of bulk carbonaceous chondrites is distinctly different from the accepted average solar value. We show that the Mo data require the presence of material produced in at least two different r-processes, and that the contribution from the p-process material is decoupled from the r-process, all occurring in supernova explosions. This is consistent with the emerging picture of diverse sources inferred from short-lived isotopes in the early Solar System and elemental analyses of metal-poor stars.     

Anomalously high δD and micro-scale hydrogen isotope heterogeneities in the mantle: Ion microprobe analysis of amiboles from peridotite xenoliths at Nushan, eastern China

Hydrogen isotopic compositions of four amphibole grains from three pieces of lherzolite xenoliths in Cenozoic basanites of Nushan, eastern China have been analyzed by ion microprobe. δD values of all analyzed points range from −94‰ to +46‰, some of which are much higher than the highest δD (+8‰) reported previously for mantle materials. The heterogeneities of D/H ratios within single grains have been observed, the variation of δD is up to 80‰ on the scale of less than 400 μm. No correlation between hydrogen isotopic ratios and hydrogen contents can be found, implying that the scatter of δD values could not result from a late shallow process such as hydrogen loss or hydrothermal alterations and should be considered as inherited from the source at depth. Chemical compositions of Nushan amphiboles are very homogeneous, excluding the fact that the scatter of δD values could arise from variable fractionation factors between a single fluid source and minerals. Therefore, metasomatic fluids responsible for the formation of Nushan amphiboles should be heterogeneous and result in the observed large variable and anomalously high δD values of amphiboles. We suggested that such metasomatic fluids could be related to magma degassing in the mantle source. Based on the D-H diffusion data and the scale of hydrogen isotope heterogeneities, it was inferred that the mantle metasomatism took place soon before the eruption of host magma.     

A non-terrestrial 16O-rich isotopic composition for the protosolar nebula

The discovery in primitive components of meteorites of large oxygen isotopic variations that could not be attributed to mass-dependent fractionation effects has raised a fundamental question: what is the composition of the protosolar gas from which the host grains formed? This composition is probably preserved in the outer layers of the Sun, but the resolution of astronomical spectroscopic measurements is still too poor to be useful for comparison with planetary material. Here we report a precise determination of the oxygen isotopic composition of the solar wind from particles implanted in the outer hundreds of nanometres of metallic grains in the lunar regolith. These layers of the grains are enriched in 16O by >20 +/- 4 per thousand relative to the Earth, Mars and bulk meteorites, which implies the existence in the solar accretion disk of reactions--as yet unknown--that were able to change the 17O/16O and 18O/16O ratios in a way that was not dependent strictly on the mass of the isotope. Photochemical self-shielding of the CO gas irradiated by ultraviolet light may be one of these key processes, because it depends on the abundance of the isotopes, rather than their masses.     

Noble-gas-rich chondrules in an enstatite meteorite

Chondrules are silicate spherules that are found in abundance in the most primitive class of meteorites, the chondrites. Chondrules are believed to have formed by rapid cooling of silicate melt early in the history of the Solar System, and their properties should reflect the composition of (and physical conditions in) the solar nebula at the time when the Sun and planets were forming. It is usually believed that chondrules lost all their noble gases at the time of melting. Here we report the discovery of significant amounts of trapped noble gases in chondrules in the enstatite chondrite Yamato-791790, which consists of highly reduced minerals. The elemental ratios 36Ar/132Xe and 84Kr/132Xe are similar to those of 'subsolar' gas, which has the highest 36Ar/132Xe ratio after that of solar-type noble gases. The most plausible explanation for the high noble-gas concentration and the characteristic elemental ratios is that solar gases were implanted into the chondrule precursor material, followed by incomplete loss of the implanted gases through diffusion over time.     

40Cr钢离子注入后表面形态变化初探

本文对40Cr钢详细测量、分析了其二维和三维的表面粗糙度,随注入能量和剂量不同各评定参数的变化趋势也不同.离子注入使粗糙度高度参数值普遍下降,间距参数值有时增大,有时减小,通过溅射作用有时使糙峰数减少,有时又产生新峰;形状参数上峰态也发生变化.对不同参数的注入表面尚进行了自相关函数和功率谱函数分析.     

惰性气体含量对深层地下水形成温度的示踪意义分析

惰性气体在地下水中的溶解量主要取决于水温和气体分压 ,而且溶解度在常见的水温范围内是水温的单调函数 .因此 ,当深层地下水系统处于封闭状态 ,系统中不存在蜕变成因或变质成因的惰性气体源时 ,可将溶解的惰性气体作为指示地下水形成温度的天然示踪剂 .     

Geochemical characteristics of light hydrocarbons in natural gases from the Turpan-Hami Basin and identification of low-mature gas

Theoretical and practical knowledge regarding low-mature gasses is of significant importance to identifying potential natural gas resources. Light hydrocarbon parameters and C and H isotopes are useful tools to identify low-mature gas. Twenty gas samples were collected from the Turpan-Hami Basin for light hydrocarbon analyses. The results showed that the light hydrocarbon components of natural gases contain high methylcycloxane, high isoparaffin and low benzene. This implies that the gas-generating parent materials are of typical humus type and the paleoenvironment is a fresh water sedimentary environment. These features are consistent with the geological setting of the basin. Comparative studies of isoheptane, heptane, and the carbon isotopic compositions of methane in natural gases, and other maturity indices indicated that natural gases in the Turpan-Hami Basin are dominated by low-mature gas formed during the low evolution stage of Jurassic coal seams. The parent materials are of type III, and the maturation degree was in the low evolution stage. These are the fundamental characteristics of low-mature gas. Results of light hydrocarbon research provided further evidence to suggest that the Turpan-Hami Basin is a large-scale gas producer of low-mature gas in China. It is likely that this resource will play an important role in future exploration and development of low-mature gas in China.