CCSD岩芯中部分石英脉的氦、氩同位素初步研究

对中国大陆科学钻探(CCSD)1700m-2300m岩芯中部分超高压变质岩中的石英脉进行了氦、氩同位素组成的初步研究,结果显示石英脉的3He／4He比值为0．37×10-6-0．98×10-6,40Ar／36Ar为498-3260,4He／40Ar为0．17-2．12, 3He／36Ar为0．81×10-4-39．38×10-4。分析结果与前人对大别-苏鲁的榴辉岩全岩和单矿物的氦、氩同位素分析结果相一致,在He-Ar相关图解上均位于地壳和地幔氦、氩同位素组成的过渡部位,表明石英脉的成矿流体中不仅有壳源稀有气体,还有幔源稀有气体。石英脉是榴辉岩的早期退变质脉,它不仅可以继承围岩超高压变质岩的氢氧稳定同位素特征,还可以继承并保存围岩的稀有气体同位素特征。     

河北汉诺坝新生代玄武岩中幔源包体和高压巨晶的氦同位素地球化学研究

对该地区新生代玄武岩中幔源包体和高压巨晶的氦同位素进行了初步研究。幔源包体中橄榄石的3 He 4 He值为 (0 .15～ 7.4)× 10 - 6,较MORB值明显偏低 ,甚至低于大气的值 ,说明该地区曾发生过强烈的地幔交代作用。高压巨晶辉石和石榴子石的氦同位素组成与此明显不同 ,其3 He 4 He值为 (5 .7～ 2 4.3)× 10 - 6。提出幔源包体和高压巨晶不是同源的 ,二者可能与寄主玄武岩均无必然成因联系。在汉诺坝地区一件石榴子石巨晶中还发现了异常高的3 He 4 He值。     

广东三水盆地天然气非烃组分同位素地球化学

根据广东省三水盆地天然气中氦、氩、二氧化碳和氮等非烃组分的稳定同位素地球化学特征,探讨了该区天然气的来源以及大地热流。测得天然气中3He/4He（R）值为（1.60-6.36）×10-6,比大气的3Ne/4He（Ra）值(1.4×10-6)大:氩的稳定同位素组成(40Ar/36Ar=450-841)较大气氩富40Ar;二氧化碳的δ13C（PDB）值在-20-2‰的范围内,δ13N（Air）值在-57-+95‰之间:根据（?）He,4He值求得研究区的大地热流值（Q）为72-82mWm-2。大地热流和非烃组分同位素组成的高值以及研究区特别发育的火山岩等地质资料表明三水盆地有较强的地球深部流体（物质的和热的）向上溢出。一些油气藏中相当一部分氦、氩和氮来自地幔,各种天然气中均混有地壳来源的非烃气体。贫13C的二氧化碳气主要为地层中有机质分解的产物;富13C的二氧化碳则主要来自岩石化学反应的产物,并混有深部来源的二氧化碳。相当一部分大地热流源于上地幔。     

柴达木盆地北缘富氦天然气的发现——兼议成藏地质条件

在柴达木盆地北缘全吉山、团鱼山地区的煤炭钻孔和泥页岩解吸气中发现了体积分数较高的氦气显示。对2个地区的6件样品进行甲烷C同位素和He同位素分析,其中2个样品的δ13C1值分别为-38.4‰和-39.9‰,属于有机成因。4个样品的3He/4He同位素测试结果在0.03×10-6~1.3×10-6之间,表明氦气来源以壳源氦为主,个别样品有少量幔源氦加入。通过区域背景资料和物探资料分析认为,柴北缘壳源成因的氦可能主要来源于基底富U、Th花岗岩体的放射性衰变,而柴北缘的山前深大断裂则可为氦的运移提供良好通道。氦气产生后,在垂向运移过程中结合其他烃类或非烃类气体,在侏罗系、古近系—新近系良好的储盖条件下,有可能形成独特的富氦天然气富集。     

鄂尔多斯盆地氦同位素的特征

鄂尔多斯盆地是中国最稳定的含油气盆地,也是我国发现1000×108m3以上大气田最多的盆地。根据46个气样氦同位素分析,3He／4He为3．1×10-8-1．2×10-7,平均为4．36×10-8,R／Ra值为0．022-0．085,是壳源氦的特征。鄂尔多斯盆地3He／4He和R／Ra值不受天然气的成因类型、气的产状及气的原生性与后生改造的影响。R／ Ra值定量说明鄂尔多斯盆地构造上极稳定。     

大别—苏鲁地区超高压变质榴辉岩的氦同位素地球化学研究

大别—苏鲁地区榴辉岩的~3He/~4He比值大部分位于0.056～0.67 Ra之间,在~3He-~4He图上位于陆壳氦与地幔氦的混合部位。碧溪岭榴辉岩的~3He/~4He比值相对较高,为5.6Ra,具幔源岩石的特点。榴辉岩的~3He含量变化较小,大部分位于1.04×10~(-12)～4.94×10~(-12)cm~3STP/g的范围之内,~4He含量变化相对较大,0.28×10~(-6)～30.47×10~(-6)cm~3STP/g;~3He/~4He值较高的样品,~4He含量相对较低;~3He/~4He值较低的样品,~4He含量相对较高。这表明榴辉岩中放射性成因~4He的积累对其~3He/~4He值有重要的影响;榴辉岩形成时的初始~3He/~4He比值较测量值应更高一些,可能更接近地幔氦的分布范围;榴辉     

广东三水盆地非烃天然气同位素地球化学

本文根据广东省三水盆地天然气中He,Ar,CO_2和N_2的稳定同位素地球化学特征,探讨了该区非烃天然气组分的成因以及大地热流。天然气中~3He/~4He值为(1.60—6.39)×10~(-6),~(40)Ar/~(36)Ar值为450—841,δ~(13)C_(Co_2)的变化范围为-20—-2‰,δ~(15)N在-58—+95‰之间。天然气同位素地球化学特征表明三水盆地有较强的地球深部流体(物质和热)向上溢出。富含非烃组分的气藏中,大部分He,Ar,N_2来自地球深部,CO_2则主要由岩石化学反应生成。烃类天然气藏中非烃组分主要来自地壳中放射性成因的~4He、~(40)Ar和有机质热分解产生的CO_2、N_(20)根据~3He/~4He值估算大地热流值(Q)为72—82mWm~(-2),其中一半以上可能来自上地幔。     

论兰坪盆地白秧坪铜(钴)矿床成因的氦氩同位素证据

对兰坪盆地白秧坪铜钴矿床围岩及流体包裹体的研究揭示,蚀变围岩中存在锂元素的高浓集异常,相对于上地壳值(20×10-6)平均富集系数为14.55;在成矿早阶段(主成矿阶段)的流体包裹体中,Li+的含量占阳离子总量的20%以上;在假定锂的丰度同地壳一致的前提下,前人依据白秧坪铜钴矿床矿物流体包裹体中He和Ar同位素值,得出成矿流体中有幔源氦加入的结论。但由于核反应6Li(n,α)3He的存在,其3He/4He值异常于正常地壳值的原因是由于矿区存在锂的元素高浓集。故笔者认为,尚无确切证据推断白秧坪铜钴矿床成矿流体中及成矿过程中有幔源氦的参与。     

冀北地区金矿床He、Ar、Pb同位素组成及其成矿物质来源

成矿物质来源一直是成矿理论研究和找矿实践的焦点问题。选择了冀北地区3个幔枝构造金矿集中区11个金矿床黄铁矿及部分围岩进行了He、Ar同位素测定。研究表明,冀北地区主要金矿的3He/4He的值域为(0.93～7.30)×10-6,平均3.55×10-6;R/Ra=0.66～4.93,平均2.53;40Ar/36Ar=426～2073,40Ar平均为8.20×10-7cm3/g,4He/40Ar平均为2.17。矿区外围片麻岩和花岗岩的3He/4He值仅为(0.001～0.55)×10-6,反映来源上有明显差别。3He和4He在He同位素浓度图上落于地幔区附近。64个Pb同位素数据表现为矿质以幔源为主,确有部分壳源物质加入。研究认为,本区成矿物质应源于地球深部,随地幔柱多级演化,深部成矿流体由地球深部迁移到浅部,期间不可避免地存在壳幔流体的混合作用,故其值域往往界于地幔和地壳之间。     

含油气盆地油气同位素地球化学研究概述①

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, 幔源氦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-低熟油同位素特征及在自然剖面上油和源岩抽提物碳同位素分馏特征及其机理。     

Diffusion kinetics of proton-induced Ne, He, and He in quartz

A natural quartz sample free of mineral and fluid inclusions was irradiated with a 200 MeV proton beam to produce spallogenic ²¹Ne, ³He and ⁴He. Temperature-dependent diffusivities of these three nuclides were then determined simultaneously by high precision stepped-heating and noble gas mass spectrometry. The outward mobility of proton-induced nuclides reflects diffusion through the quartz lattice. In the studied range of 70 to 400°C the helium diffusion coefficients exceed those of neon by 5-7 orders of magnitude. The implied diffusion parameters E_a = 153.7 ± 1.5 (kJ/mol) and ln(D_o/a²) = 15.9 ± 0.3 (ln(s⁻¹)) and E_a = 84.5 ± 1.2 (kJ/mol) and ln(D_o/a²) = 11.1 ± 0.3 (ln(s⁻¹)) for proton-induced ²¹Ne and ³He, respectively, indicate that cosmogenic neon will be quantitatively retained in inclusion-free quartz at typical Earth surface temperatures whereas cosmogenic helium will not. However, the neon diffusion parameters also indicate that diffusive loss needs to be considered for small (<1 mm) quartz grains that have experienced elevated temperatures. Since natural quartz often contains fluid inclusions which may enhance noble gas retentivity, these parameters likely represent an end-member case of purely solid-state diffusion. The ∼70 kJ/mol higher activation energy for neon diffusion compared to helium diffusion likely represents an energy barrier related to its ∼13% greater diameter and provides a fundamental constraint with which to test theories of solid state diffusion. The diffusion parameters for proton-induced ⁴He are indistinguishable from those for ³He, providing no evidence for the commonly expected inverse square root of the mass diffusion relationship between isotopes. We also find preliminary indication that increased exposure to radiation may enhance neon and helium retentivity in quartz at low temperatures.     

~3He/~4He比值质谱计的研制与应用

本文介绍了本课题组研制的国内第一台用于地学气体样品测定的NG 10 0 0型3 He/ 4He比值质谱计。该质谱计具有小的静态容积 ,分辨率和灵敏度高及重现性等良好的分析性能。利用该质谱计测定了我国一些地区气体样品中的3 He/ 4He、4He/ 2 0 Ne比值。所分析的3 He/ 4He结果与VG 5 40 0型、MM 5 40 0型质谱计外检结果相符。     

Identification of He sources and estimation of He ages in groundwater of the North China Plain

Dissolved helium concentrations and ³He/⁴He ratios were measured for 18 groundwater samples collected from the Quaternary confined aquifers in the North China Plain (NCP). The dissolved helium concentrations ranged from 1 × 10⁻⁷ to 1 × 10⁻⁶ cm³STP·g⁻¹ in the 14 samples from the central plain, but was approximately two orders of magnitude higher, between 6 × 10⁻⁶ and 9 × 10⁻⁵ cm³STP·g⁻¹, in 4 samples from the coastal plain. Based on these concentrations and the corresponding ³He/⁴He ratios varying from 0.09 to 0.55 R_a (where R_a is the ³He/⁴He ratio of air), the dissolved helium in groundwater in the central plain was identified to be primarily a mixture of atmospheric helium with radiogenic helium and a representative radiogenic helium ratio was estimated to be 0.035 R_a. Despite the high fraction of terrigenic ⁴He in the samples from the coastal plain, their ³He/⁴He ratios were found to be significantly above this radiogenic value, ranging between 0.20 and 0.37 R_a, indicating the presence of a mantle-derived He component in this area. About 2–4% mantle helium was estimated to be present in the groundwater of the coastal plain, which probably is associated with the regional Cangdong fault and tectonic activities. Based on the radiogenic He component, ⁴He ages of the groundwater in the central plain were calculated by assuming either pure in situ production or an external helium flux J₀ of 4.7 × 10⁻⁸ cm³STPcm⁻²a⁻¹. The estimated ⁴He ages fall between 9.5 and 51.4 ka and are comparable to the ¹⁴C ages, suggesting that the results of ⁴He dating are reasonable and can be an effective tool to estimate groundwater residence times under suitable conditions.     

Controls on pore-fluid concentration of He and Rn and the calculation of He/Rn ages

Controls governing the production of ⁴He and ²²²Rn in the solid phase as well as parameters and processes contributing to their transport into the pore fluid are discussed. ²²²Rn activity is used to quantify the uranium sources for ⁴He and the result is a simplified pore-fluid age equation which is virtually independent of the porosity, the water/rock ratio, the rock density and the uranium concentration, but does require a Th/U estimate. The crucial parameter is the ratio of the release factors for the two species, /GL_Rn//GL_He, which is discussed in terms of three possible release mechanisms: (1) recoil; (2) recoil followed by diffusion; and (3) weathering release of accumulated ⁴He. It was found that /GL_Rn//GL_He can vary over several orders of magnitude, but can be expressed in terms of the effective grain size r, and the diffusive half-length for ²²²Rn decay, r_e.⁴He measurements are used to “date” gases from known gas fields and the agreement with the assumed source-rock age is good. Application of ⁴He/ ²²²Rn measurements to continental freshwater springs indicates that the weathering release of accumulated ⁴He dominates the input and results in a large overestimate of groundwater age. Measurement in the Lardarello geothermal field indicates that the ⁴He/²²²Rn method can indicate relative transport direction. Other possible applications in various geochemical fields are suggested.     

Grain boundary partitioning of Ar and He

An experimental procedure has been developed that permits measurement of the partitioning of Ar and He between crystal interiors and the intergranular medium (ITM) that surrounds them in synthetic melt-free polycrystalline diopside aggregates. ³⁷Ar and ⁴He are introduced into the samples via neutron irradiation. As samples are crystallized under sub-solidus conditions from a pure diopside glass in a piston cylinder apparatus, noble gases diffusively equilibrate between the evolving crystal and intergranular reservoirs. After equilibration, ITM Ar and He is distinguished from that incorporated within the crystals by means of step heating analysis. An apparent equilibrium state (i.e., constant partitioning) is reached after about 20 h in the 1450 °C experiments. Data for longer durations show a systematic trend of decreasing ITM Ar (and He) with decreasing grain boundary (GB) interfacial area as would be predicted for partitioning controlled by the network of planar grain boundaries (as opposed to ITM gases distributed in discrete micro-bubbles or melt). These data yield values of GB-area-normalized partitioning, , with units of (Ar/m³ of solid)/(Ar/m² of GB) of 6.8 × 10³-2.4 × 10⁴ m⁻¹. Combined petrographic microscope, SEM, and limited TEM observation showed no evidence that a residual glass phase or grain boundary micro-bubbles dominated the ITM, though they may represent minor components. If a nominal GB thickness (δ) is assumed, and if the density of crystals and the grain boundaries are assumed equal, then a true grain boundary partition coefficient , may be determined. For reasonable values of δ, is at least an order of magnitude lower than the Ar partition coefficient between diopside and melt. Helium partitioning data provide a less robust constraint with between 4 × 10³ and 4 × 10⁴ cm⁻¹, similar to the Ar partitioning data. These data suggest that an ITM consisting of nominally melt free, bubble free, tight grain boundaries can constitute a significant but not infinite reservoir, and therefore bulk transport pathway, for noble gases in fine grained portions of the crust and mantle where aqueous or melt fluids are non-wetting and of very low abundance (i.e., <0.1% fluid). Heterogeneities in grain size within dry equilibrated systems will correspond to significant differences in bulk rock noble gas content.     

^3He／^4He Ratios and Heat Flow in the Continental Rift—valley,Eastern China

Heat flow and the origin of helium in natural gases from fault basins of the continental rift-valley in eastern China are discussed in terms of helium isotope geochemistry.³He/⁴He ratios in natural gases from the rift-valley range from 2.23 × 10⁻⁷ to 7.21 × 10⁻⁶, which are directly proportional to the concentration of helium and ΣNHC/ΣHC ratio in natural gases. Geological and isotope geochemical data suggest that helium in natural gases consists predominantly of crustal radio-genic and upper mantle-derived helium. In a simple mixing pattern between crustal He and mantle-derived He, mantle-derived helium in natural gases would account for 10–60%. Calculated values for heat flow (Q) range from 59.7 to 82.4mWm⁻², of which about 60 percent in the rift-valley is derived from the upper mantle. Natural helium reservoirs would be found in the areas where the upper mantle uplifted greatly and heat flow is large in the continental rift-valley. The project is financially supported by the National Natural Science Foundation of China.     

4He diffusion in specular hematite

In order to test the chronometer qualities of speculante for the (U + Th)/He dating method, ⁴He release experiments by stepwise heating of two specularites from the Rimbach mineralization locality in the southern Vosgues (France) have been carried out. The diffusion coefficients define linear Arrhenius plots within a temperature interval of 250 to 830 °C, which is suggestive of volume diffusion. Extrapolation of the diffusion behavior to 20° C yields diffusion coefficients (D₂₀ values) smaller than 10^?26 [cm² s^?1] for both hematites with activation energies at 116 [kJ/mole]. The results of our study suggest that specularite is a very helium retentive hematite variety which is capable of quantitatively retaining radiogenic helium over geologic periods of time.     

Zircon (U-Th)/He thermochronometry: He diffusion and comparisons with Ar/Ar dating

(U-Th)/He chronometry of zircon has a wide range of potential applications including thermochronometry, provided the temperature sensitivity (e.g., closure temperature) of the system be accurately constrained. We have examined the characteristics of He loss from zircon in a series of step-heating diffusion experiments, and compared zircon (U-Th)/He ages with other thermochronometric constraints from plutonic rocks. Diffusion experiments on zircons with varying ages and U-Th contents yield Arrhenius relationships which, after about 5% He release, indicate E_a = 163-173 kJ/mol (39-41 kcal/mol), and D₀ = 0.09-1.5 cm²/s, with an average E_a of 169 ± 3.8 kJ/mol (40.4 ± 0.9 kcal/mol) and average D₀ of 0.46^+0.87_−0.30 cm²/s. The experiments also suggest a correspondence between diffusion domain size and grain size. For effective grain radius of 60 μm and cooling rate of 10°C/myr, the diffusion data yield closure temperatures, T_c, of 171-196°C, with an average of 183°C. The early stages of step heating experiments show complications in the form of decreasing apparent diffusivity with successive heating steps, but these are essentially absent in later stages, after about 5-10% He release. These effects are independent of radiation dosage and are also unlikely to be due to intracrystalline He zonation. Regardless of the physical origin, this non-Arrhenius behavior is similar to predictions based on degassing of multiple diffusion domains, with only a small proportion (<2-4%) of gas residing in domains with a lower diffusivity than the bulk zircon crystal. Thus the features of zircon responsible for these non-Arrhenius trends in the early stages of diffusion experiments would have a negligible effect on the bulk thermal sensitivity and closure temperature of a zircon crystal.We have also measured single-grain zircon (U-Th)/He ages and obtained ⁴⁰Ar/³⁹Ar ages for several minerals, including K-feldspar, for a suite of slowly cooled samples with other thermochronologic constraints. Zircon He ages from most samples have 1 σ reproducibilities of about 1-5%, and agree well with K-feldspar ⁴⁰Ar/³⁹Ar multidomain cooling models for sample-specific closure temperatures (170-189°C). One sample has a relatively poor reproducibility of ∼24%, however, and a mean that falls to older ages than predicted by the K-feldspar model. Microimaging shows that trace element zonation of a variety of styles is most pronounced in this sample, which probably leads to poor reproducibility via inaccurate α-ejection corrections. We present preliminary results of a new method for characterizing U-Th zonation in dated grains by laser-ablation, which significantly improves zircon He age accuracy.In summary, the zircon (U-Th)/He thermochronometer has a closure temperature of 170-190°C for typical plutonic cooling rates and crystal sizes, it is not significantly affected by radiation damage except in relatively rare cases of high radiation dosage with long-term low-temperature histories, and most ages agree well with constraints provided by K-spar ⁴⁰Ar/³⁹Ar cooling models. In some cases, intracrystalline U-Th zonation can result in inaccurate ages, but depth-profiling characterization of zonation in dated grains can significantly improve accuracy and precision of single-grain ages.     

Low-energy 3He and 4He ions in interplanetary space during quiet periods of the 23rd solar cycle

Data from the ULEIS instrument aboard the ACE spacecraft are used to study the energy spectra of ³He and ⁴He ions produced during periods of the quiet Sun in the 23rd solar cycle in the energy range ～0.08–2 MeV/nucleon. Differences in the spectra and ³He/⁴He relative abundances for three groups of quiet periods dominated by different sources of ions are demonstrated: weak impulsive solar flares, particles of the solar corona, and solar wind particles accelerated to energies of several MeV/nucleon.