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.     

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.     

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.     

滇西富碱斑岩型多金属矿稀有气体同位素组成特征及地质意义*

通过对滇西富碱斑岩型多金属矿区稀有气体同位素组成的研究表明,黄铁矿和石英脉等流体包裹体中3He/4He值主要为0.160 8~3.470 0 Ra,远高于地壳特征值,而整体略低于地幔特征值;20Ne/22Ne和21Ne/22Ne平均值分别为11.271和0.032 2,接近地幔同位素组成;40Ar/36Ar和38Ar/36Ar平均值分别为395.51和0.197 6,均高于大气比值,而低于MORB比值;128~136Xe/130Xe值与大气相比均表现出过剩的特征。综合研究表明,滇西多金属矿区包裹体中稀有气体同位素组成在显示含矿流体的幔源特征的同时,又表现出强烈的地壳特征;成矿流体主要源于深部地幔,在参与交代蚀变过程中,其性质由熔浆向热液过渡,同时引发壳幔物质叠加混染,正是这种流体作用构成了滇西新生代富碱斑岩多金属成矿的内在统一制约因素。     

Noble gas abundances and isotopic compositions in mantle-derived xenoliths, NE China

Following the researches of helium isotopic compositions in mantle-derived xenoliths in eastern China,this study reported noble gas abundances and isotopic compositions of mantle-derived xenoliths from Kuandian of Liaoning Province, Huinan of Jilin Province and Hannuoba of Hebei Province. Compared with the middle ocean ridge basalt (MORB) and other continental areas, mantle-derived xenoliths in NE China are characterized by slightly low noble gas abundances, 3He/4He equivalent to or lower than that of MORB, 40Ar/36Ar lower than that of MORB, 38Ar/36Ar and Ne-Kr-Xe isotopic ratios equivalent to those of atmosphere. These results indicate the heterogeneity of subcontinentai lithospheric mantle beneath northeastern China, that is, a MORB reservoir-like mantle beneath Kuandian and an enriched/metasomatized mantle beneath Huinan. Low 40Ar/36Ar ratios in the three studied areas may imply that a subducted atmospheric component has been preserved in the subcontinental lithospheric mantle.``     

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 .     

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.     

He and Ar isotopes in mantle megacryst minerals from Nushan and Yingfengling in Southeast China

He and Ar isotopic compositions of megacrystal minerals from mantle xenoliths were measured by the technique of vacuum crushing extraction. The used samples were clinopyroxene, garnet and ilmenite in Cenozoic alkaline basalts, which were from Nushan in Anhui Province and Ying-fengling in Guangdong Province, respectively, and represented materials from the upper mantle in the continental margin of SE China. The results show ^3He/^4He ratios of 7.99 Ra to 8.58 Ra, consistent with the characteristic ratios of the MORB-type mantle. ^40Ar／^39Ar ratios vary from 313 to 909, suggesting a binary mixing between the MORB-type mantle and air argons. This may reflect the incorporation of the air argon absorbed in oceanic sediments into the mantle beneath the continental margin by subduction of oceanic plate. This study presents the first report that ilmenite megacrysts contain abundant fluid inclusions and noble gases in the mantle xenoliths.     

Cosmic-ray exposure and gas retention ages of the Guangmingshan (H5) chondrite

Isotopic compositions of noble gases from the Guangmingshan chondrite were analyzed. Based on the analyses of cosmogenic nuclei, cosmic-ray exposure age of the meteorite is (65±10.0) Ma (³He), (80±12) Ma (²¹Ne) and (65±10.0) Ma (³⁸Ar), with an average of 70 Ma. This is the highest exposure age of H-group ordinary chondrites. Gas retention ages of K-Ar and U, Th-⁴He are (4230±100) Ma and (3300±60) Ma, respectively. The smaller ages of³He than²¹Ne and⁴He than⁴⁰Ar suggest that both³He and⁴He lost together. This is probably related to a solar heating effect of a meteorite with a small perihelion during the last exposure period.     

Early differentiation and volatile accretion recorded in deep-mantle neon and xenon

The isotopes (129)Xe, produced from the radioactive decay of extinct (129)I, and (136)Xe, produced from extinct (244)Pu and extant (238)U, have provided important constraints on early mantle outgassing and volatile loss from Earth. The low ratios of radiogenic to non-radiogenic xenon ((129)Xe/(130)Xe) in ocean island basalts (OIBs) compared with mid-ocean-ridge basalts (MORBs) have been used as evidence for the existence of a relatively undegassed primitive deep-mantle reservoir. However, the low (129)Xe/(130)Xe ratios in OIBs have also been attributed to mixing between subducted atmospheric Xe and MORB Xe, which obviates the need for a less degassed deep-mantle reservoir. Here I present new noble gas (He, Ne, Ar, Xe) measurements from an Icelandic OIB that reveal differences in elemental abundances and (20)Ne/(22)Ne ratios between the Iceland mantle plume and the MORB source. These observations show that the lower (129)Xe/(130)Xe ratios in OIBs are due to a lower I/Xe ratio in the OIB mantle source and cannot be explained solely by mixing atmospheric Xe with MORB-type Xe. Because (129)I became extinct about 100 million years after the formation of the Solar System, OIB and MORB mantle sources must have differentiated by 4.45 billion years ago and subsequent mixing must have been limited. The Iceland plume source also has a higher proportion of Pu- to U-derived fission Xe, requiring the plume source to be less degassed than MORBs, a conclusion that is independent of noble gas concentrations and the partitioning behaviour of the noble gases with respect to their radiogenic parents. Overall, these results show that Earth's mantle accreted volatiles from at least two separate sources and that neither the Moon-forming impact nor 4.45 billion years of mantle convection has erased the signature of Earth's heterogeneous accretion and early differentiation.     

苏北盆地朱家墩气田气源追溯

对于苏北盆地盐城凹陷朱家墩气田的气源存在多种不同看法,但均无气/源对比的直接证据加以证明.作者借助天然气轻烃指纹气相色谱分析方法以及岩石轻烃指纹气相色谱分析方法进行直接的气/源对比,研究结果证实朱家墩气田的天然气为混源气,以海相油型裂解型干气为主,渗混了海、陆相混源型油型高熟气.     

History of trace gases in presolar diamonds inferred from ion-implantation experiments

Diamond grains are the most abundant presolar grains found in primitive meteorites. They formed before the Solar System, and therefore provide a record of nuclear and chemical processes in stars and in the interstellar medium. Their origins are inferred from the unusual isotopic compositions of trace elements-mainly xenon-which suggest that they came from supernovae. But the exact nature of the sources has been enigmatic, as has the method by which noble gases were incorporated into the grains. One observation is that different isotopic components are released at different temperatures when the grains are heated, and it has been suggested that these components have different origins. Here we report results of a laboratory study that shows that ion implantation (previously suggested on other grounds) is a viable mechanism for trapping noble gases. Moreover, we find that ion implantation of a single isotopic composition can produce both low- and high-temperature release peaks from the same grains. We conclude that both isotopically normal and anomalous gases may have been implanted by multiple events separated in space and/or time, with thermal processing producing an apparent enrichment of the anomalous component in the high-temperature release peak. The previous assumption that the low- and high-temperature components were not correlated may therefore have led to an overestimate of the abundance of anomalous argon and krypton, while obscuring an enhancement of the light-in addition to the heavy-krypton isotopes.     

Carbon and hydrogen isotopic compositions and their evolutions of gases generated by herbaceous swamp peat at different thermal maturity stages

Coalbed methane (CBM) accumulation models include continuous gas accumulation and staged gas accumulation.However,studied on the geochemical characteristics and indices to evaluate staged accumulation CBM are lacking.This study for the first time obtained the carbon and hydrogen isotopic compositions of methane and ethane generated at different evolution stages using thermal simulation of samples prepared by treating an herbaceous swamp peat at different temperatures.The results showed that the carbon isotopic compositions of methane and ethane were obviously affected by the thermal evolution level of the starting sample,while the hydrogen isotopic compositions were closely related to the maturity of gases.The carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter with Ro values from 1.2%,1.7%,2.4%,3.2% and 3.7% to 5.2% were determinated.The relationship between Ro values and the carbon and hydrogen isotopic compositions of gases generated by coal-forming organic matter at different evolution stages as well as the carbon or hydrogen isotopic relationships between methane and ethane were established.The results provide a scientific basis for studying the genesis of CBM generated at different maturity intervals and understanding the geochemical characteristics of staged accumulation CBM.These results were applied to a case study on CBM from the southern Qinshui basin,and it was found that the CBM accumulated after the Middle Jurassic and was characteristic of staged gas accumulation.This is consistent with the result of geological studies,and further showed that the results of thermal simulation experiments are very important for evaluating the genesis of natural CBM.     

Natural gas geochemistry of low evolutionary stage of medium- and small-sized basins in Yunnan Province, southwestern China

The biogenic gas and premature-low mature associated gases in some medium and small-sized basins of Yannan Province, such as Luliang, Yanglin, Baoshan and Jinggu basins, have beed researched. The results show that the biogenic-gas consists mainly of methane which is more than 99% in gasous hydrocarbons and of lighter carbon isotopic composition with δ13C1 values from -60.0‰ to - 75.4‰. The methane carbon isotopic compositions in the Baoshan Basin is relatively heavy (δ13C1 - 60‰- - 65‰), but those in Luliang and Yanglin basins are lighter (δ13C1, less than -70‰), which implies that the gas field of the Baoshan Basin formed earlier than the others. In the Jinggu Basin, where crude oil is premature-lower mature, the natural gas of associated oil relatively wet and the relative content of methane about 58%-95% in gasous hydrocarbons. Constituently the gas composition is much similar to associated one, but the methane carbon isotopic compositions from - 53.8‰ to - 57.8‰ are obviously richer in 12C than those of general oil fields and similarly characterize the biothermo-catalytic transitional zone gas. Their ethane carbon isotopic compositions from - 34.6‰ to -29.0‰ show that they may be derived from type Ⅰ or Ⅱ source rock. But for the associated gas from lower evolutionary stage, the heavier ethane carbon isotopic composition as well as the reversed order among the carbon isotopic composition of ethane, propylane and butane also implies that some gases from the type Ⅲ organic matter are mixed. The δ13CCo2 of the samples essentially less than - 10‰ may be generated from organic matter.     

稀有气体原子插入N—H和O—H键的理论研究

采用B3LYP方法在6-311++G**基组(Ar,Kr,Xe采用DZVP基组)水平上对稀有气体原子X(X=Ar,Kr,Xe)插入咪唑、吡咯、吡唑中的N—H键进行了量子化学理论研究.优化得到了9种稳定的含稀有气体原子的化合物;插入稀有气体原子后体系的能量升高了398.11~815.02 kJ/mol,且新形成的H—X键强度与正常氢键相当,X—N化学键强度比正常氢键略弱,因此引入X原子后的产物热稳定性较差.电子密度拓扑研究表明:N—H键插入X原子后,激活了咪唑、吡咯、吡唑杂环官能团上的反应活性.     

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.     

C60的惰性气体原子化合物分子力学研究

利用分子间相互作用势模型对惰性气体原子在Ｃ６０分子内所形成的化合物进行了研究，讨论了惰性气体原子Ｘ的平衡位置及体系的稳定性，Ｈｅ，Ｎｅ和Ａｒ原子的平衡位置在Ｃ６０笼的中心，而Ｋｒ和Ｘｅ原子则在Ｃ６０笼外比在其内部时体系更稳定，通过考察其附加原子半径大小，可以对附加原子与Ｃ６０笼能否形成稳定的化合物提供预见性。     

6—30keV单电荷离子与H2分子碰撞的单电子剥离截面的测量

用增长率方法测量了６－３０ｋｅＶＨｅ＾＋，Ｎｅ＾＋，Ａｒ＾＋，Ｋｒ＾＋，Ｘｅ＾＋及Ｃｌ＾＋离子与Ｈ２分子碰撞的单电子剥截面，Ｈｅ＾＋的截面数量与他人数据一致，其他的截面数据在此之前未见报道。     

降雨入渗条件下土壤水同位素变化实验

 通过输入比初始土壤水富集轻同位素且同位素组成稳定的降雨进行室内降雨入渗实验,研究土壤水氢氧同位素在土壤中变化情况。实验结果表明,降雨在入渗过程中,降雨同位素与初始土壤水同位素发生混合稀释,出流同位素组成随时间减小,最后趋于稳定,接近降雨同位素组成;出流氢氧同位素关系线斜率由以初始土壤水和降雨同位素组成为端点的混合线斜率决定;通过曲线拟合出流同位素随时间的变化函数关系,确定其传递函数分布为指数-活塞流模型分布,且氢同位素和氧同位素的传递函数相同。     

Kinetic study of hydrocarbon generation of oil asphaltene from Lunnan area, Tabei uplift

The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature probably made remarkable contributions to natural gas from Lunnan area.