异构比φiC4/φnC4和φiC5/φnC5的石油地质意义

同分子量的正构烷烃和异构烷烃存在着物理化学性质差异,在运移过程中受围岩的物理化学性质及其它外部因素的影响必然产生分异效应,从而使二者在空间分布上具有一定的特征和规律,异构比指标可以在一定程度上反映出这种特征和规律性.用异构比φiC4/φnC4和φiC5/φnC5指标可以判断有机质的成熟度,研究轻烃运移的途径、方向、生成环境及轻烃的生物降解.     

洛川黄土剖面末次冰期间冰段弱古土壤 (L1 SS1)分子化石及其古植被与古环境*

利用气相色谱-质谱联用仪(GC-MS)对连续取样的洛川黄土剖面弱古土壤层(L₁ SS₁)和相邻黄土层(L₁LL₁,L₁LL₂)的分子化石进行了检测,获得正构烷烃、正烷基-2-酮和酰胺等种类众多、丰度较高的分子化石。W_草/植=nC₃₁/(nC₂₇+nC₂₉+nC₃₁),W_木/植=(nC₂₇+nC₂₉)/(nC₂₇+nC₂₉+nC₃₁)和W_木/草=(nC₂₇+nC₂₉)/nC₃₁记录了草本与植被、木本与植被、木本与草本比例变化规律的古植被信息。检测样品的CPI值为5.60~11.50,地质作用影响较小;通过磁化率、粒度和分子化石指标的相关性分析,认为磁化率、粒度记录了环境变化及主要气候事件(相关系数达-0.81);而分子化石能较好地反映古植被变化。当气候环境由干冷向温湿变化、水热配置条件改善时,植被变化响应较迅速;当环境恶化、转向干冷时,响应较弱或滞后,这种现象可能是由于植被生态系统稳定性造成的结果。整个研究剖面段样品以nC₃₁为主峰的高碳数优势,分子化石表明末次冰期间冰段洛川地区(黄土高原)发育草本植被而没有出现以森林为主的植被。     

若尔盖高原沼泽湿地CH4排放研究

若尔盖高原沼泽湿地海拔 3400 m，面积 4038km²，是我国面积最大的高原沼泽湿地分布区。2001年 5～9月的非冰冻期，其主要沼泽类型木里苔草沼泽的CH₄排放通量范围是 0.51～ 8.20 m g/（m ²· h），平均值为 2.87 m g/（m ²· h）；乌拉苔草沼泽CH₄排放通量范围是 0.36～10.04 m g/（m ²· h），平均值为 4.51 m g/（m ²· h）。在空间分布上，不同沼泽类型之间CH₄排放通量具有一定的差异。在季节变化上，没有明显的排放高峰。根据代表性观测点的CH₄平均排放量、日数和沼泽总面积推算，非冰冻期若尔盖高原沼泽湿地CH₄的排放量为 0.052Tg/a。     

陕西长武黄土剖面L3～S6土层渗透性研究

根据渗水实验、孔隙度、粒度、磁化率测定,研究了长武黄土剖面L₃～S₆土层的渗透性及其成因。研究结果表明,L₃,L₄,L₅和L₆黄土层渗透性较强,稳定入渗速率较高,它们的渗透系数变化在0.57～1.06mm/分之间,4层平均为0.75mm/分;S₃,S₄,S₅和 S₆古土壤渗透性较弱,稳定入渗率较低,它们的渗透系数变化在0.18～0.71mm/分之间,4层平均为0.44mm/分。红色古土壤达到稳定入渗率的时间一般比黄土层要长;   黄土层的平均空隙度比红褐色古土壤高,渗透性强,粒度成分较粗,黄土层比红褐色古土壤层更利于构成含水层;   红褐色古土壤层粒度成分细,空隙度低,渗透性弱,比黄土层利于形成隔水层。长武第4层古土壤厚度小,纵向裂隙发育强,入渗速率较大,不易形成隔水层。磁化率、粘粒含量资料表明红褐色古土壤层与黄土层渗透性、含水空间和隔水性的差异主要是当时气候冷干和温湿交替变化的结果。     

C3、C4植物及其硅酸体研究的古生态意义

本文概述了C₃、C₄植物生理、生态学意义、地理分布及其相应的植物硅酸体形态,进一步讨论了C₃、C₄植物硅酸体形态在我国表层土壤中的分布规律及生态学意义。最后,对洛川黑木沟全新世黄土剖面中C₃、C₄植物硅酸体形态变化特点做了分析,表明地层中典型的C₃、C₄植物硅酸体形态,作为古植物的直接证据,可以较准确地反映古植被、古环境的变化规律。     

K-H3OFe3(SO4)2(OH)6铁矾的XRD研究

根据X射线衍射(XRD)分析发现: A Fe₃(SO₄)₂(OH)₆(A=K⁺、H₃O⁺)系列铁钒的XRD数据十分相近,难以用XRD区别,需通过能谱(EDS)辅助分析,才能区分此类铁矾。另外,此类铁矾的003和107面网间距d随K⁺含量增大而增大,且呈一元三次方程的关系;而033和220面网间距d随K⁺含量增大而减小,呈一元二次方程的关系。对该现象从铁矾晶体结构方面进行解释:K⁺、H₃O⁺离子位于较大空隙中,且沿着Z轴方向排列,当K⁺、H₃O⁺离子之间相互替换时,会导致该铁矾晶体结构在Z轴方向有较明显的变化。     

湖泊沉积物C4植物含量重建方法的讨论——以新生代柴达木盆地大红沟剖面为例

当前气候变暖是一个全球面临的重大问题,它对人类赖以生存的植被生态系统造成的影响已经在全球各地逐步显现出来。为了深入了解植物生态系统对环境和气候变化的响应机制,我们需要更好地借鉴地质历史时期气候环境和植物协同演化的重要事件。C₄植物作为陆地生产力较强的植物,在植物生态演化中占举足轻重的地位。目前研究表明C₄植物可能最晚起源于始新世-渐新世之交,但从它早期起源到随后在生态系统中的大规模扩张时间间隔长达20多个百万年。是什么因素导致了C₄植物的起源和扩张是一个悬而未决的重要问题,需要开展大量的调查研究来评估和重建C₄植物在过去生态系统中的相对生物量变化。重建C₄植物的含量目前主要的方法是建立在C₃/C₄植物碳同位素和植物内部结构形态差异基础之上。最常运用的研究材料包括(古)土壤有机质、成壤碳酸盐、陆地食草动物体组织、沉积物生物标志物、孢粉、植硅体等。这些方法在重建现代以及地质历史时期C₄植物相对生物量变化的研究中发挥了重要作用,但同时也存在很多无法避免的问题。本文介绍了C₄植物起源和扩张机制的主流观点以及不同研究材料的碳同位素所推算C₄植物生物量的基本原理,并以柴达木盆地大红沟剖面为例,针对新生代湖泊沉积物中陆生高等植物的长链正构烷烃特征和单体烃碳同位素的研究结果,详细讨论C₄植物含量重建的方法与缺点,为探讨C₄植物起源、演化及控制因素提供参考。我们通过分析前人研究的大红沟剖面长链正构烷烃及单体烃 δ¹³C_alk 值特征,推测在30~24 Ma、20~17 Ma和13~7 Ma期间δ¹³C_alk值显示相对正偏的原因,可能是干旱和C₄植物在当地生态系统中出现的双重因素叠加造成的。但这一推断还需要借助于新的研究方法,即单颗粒孢粉碳同位素的方法来提供C₄植物的确凿证据。     

黄土高原S5古土壤形成期的气候环境——陆生蜗牛化石的证据

通过对黄土高原西峰黄土剖面S5古土壤层的蜗牛化石组合研究发现,西峰地区在S5形成时（对应海洋氧同位素MIS₁5¹3期）气候环境经历了几次显著的波动。MIS₁5期地层中绝大多数蜗牛壳体被溶蚀,气候非常暖湿,夏季风强盛;MIS₁4是个弱冰期,蜗牛组合显示气候以凉湿为主,仍然有较强的夏季风影响;MIS₁3期以暖湿的气候为主,夏季风增强。对温湿蜗牛种类冠状砂螺（Gastrocopta coreana）含量变化的功率谱分析显示出明显的23ka周期,表明岁差轨道驱动的低纬太阳辐射是控制黄土高原夏季风变化的主导因素;冷干种类杂色虹蛹螺（Pupilla aeoli）含量变化具有明显的100ka和弱的43ka周期,说明即使在气候特征总体暖湿的背景下,冬季风仍具有以全球冰量（100ka）为主导周期的变化特征。在海洋和冰芯记录中MIS₁3和MIS₁5时期并不是最温暖的间冰期,但在黄土高原受到强夏季风的持续影响,这可能与此时北半球夏季太阳辐射量的增强和北大西洋深层流强度的加强有关。S5中S5SS₁与S5SS3两层强烈发育的古土壤可能有着不同的发育机制,S5SS₁因其较发育的母质、超长的成壤期,形成了比S5SS3更强的成壤特征。分析认为全球冰量与轨道驱动的北半球太阳辐射对MIS₁5¹3时期黄土高原气候环境的演替和冬、夏季风的消长起了主导作用。     

中国东部CO2气地球化学特征及其气藏分布

中国东部CO₂气田(藏)发育广泛,分布复杂。本文对中国东部松辽、渤海湾、苏北、三水、东海、珠江口、莺琼、北部湾等盆地和内蒙古商都地区以及部分现代构造岩浆活动区CO₂气田(藏)和气苗中CO₂的地球化学特征进行了分析和研究,探讨了中国东部CO₂气的成因、来源及分布。中国东部CO₂气的含量主要分布区间为0~10%,其次为90%~100%,呈现典型的U字型。δ¹³C_CO2值则呈现典型的单峰式分布,峰值区间为-6‰~-4‰。CO₂含量、δ¹³C_CO2值和R/Ra值综合表明,中国东部高含CO₂气以幔源无机成因为主,混有部分有机成因气和(或)壳源无机气。中国东部已发现的36个无机成因CO₂气田(藏)在空间分布上与新近纪及第四纪北西西向玄武岩活动带展布一致,深大断裂和岩浆活动是无机成因CO₂富集、运移和分布最重要、最直接的两大主控因素。     

根据井中矿层天然放射性强度利用回归分析方法计算P2O5 及Na2SO4 品位

本文介绍根据井中磷矿天然伽玛强度利用回归分析方法计算P₂O₅品位,顺便也谈谈在钙芒硝矿上的应用效果,以此说明统计分析方法应用在物探测井工作中的必要性和有效性。     

Light hydrocarbons geochemistry of surface sediment from petroliferous region of the Mehsana block,North Cambay Basin

A study was carried out to test the usefulness of surface geochemical methods as regional evaluation tools in petroliferous region of the Mehsana block, North Cambay Basin. A suite of 135 soil samples collected from the depth of 2.5 m, were analyzed for adsorbed light gaseous hydrocarbons and carbon isotopes (δ¹³C_methane and δ¹³C_ethane). The light gaseous hydrocarbon analysis show that the concentration ranges 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb of C₁, C₂, C₃, iC₄ and nC₄, respectively. The value of carbon isotopic ranges of methane −29.5 to −43.0‰ (PDB) and ethane −19.1 to −20.9‰ (PDB). This data, when mapped, indicates patterns coinciding with major known oil and/or gas field of Sobhasan/Linch in this study area. The existence of un-altered petroliferous microseeps of catagenetic origin is observed in the study area. A regional study, such as the one described here, can provide important exploration facts concerning the regional hydrocarbon potential in a block. This method has been confirmed and can be applied successfully in frontier basins.     

Geo-microbial prospecting studies of surface sediments from petroliferous region of the Mehsana Block,North Cambay Basin

Surface adsorbed gas surveys and geo-microbiological surveys are well known techniques of petroleum exploration and aim towards risk reduction in exploration by way of identifying the areas warm with hydrocarbons and to establish inter-se exploration priorities amongst the identified warm areas. The thermogenic surface adsorbed gaseous hydrocarbons distribution patterns in petroliferous areas are considered to be a credible evidence for the upward migration of hydrocarbons. The present investigation aims to explore correlation between the adsorbed gas distribution pattern and microbial oxidizers in identifying the upward migration of hydrocarbons especially in the tropical black soil terrain of known petroliferous Mehsana Block of North Cambay Basin, India. A set of 135 sub-soil samples collected, were analyzed for indicator hydrocarbon oxidizing bacteria, adsorbed light gaseous hydrocarbons and carbon isotope ratios (¹³C_methane and δ¹³C_ethane). The microbial prospecting studies showed the presence of high bacterial population for methane (5.4 × 10⁶ cfu/gm), ethane (5.5 × 10⁶ cfu/gm), propane (4.6 × 10⁶ cfu/gm) and butane oxidizing bacteria (4.6 × 10⁶ cfu/gm) in soil samples. The light gaseous hydrocarbon analysis showed that the concentration ranges of C₁, C₂, C₃, iC₄ and nC₄ are 402 ppb, 135 ppb, 70 ppb, 9 ppb and 18 ppb, respectively, and the value of carbon isotope ranges of methane ?29.5 to ?43.0‰ (V-PDB) and ethane ?19.1 to ?20.9‰ (V-PDB). The existence of un-altered petroliferous microseep (δ¹³C, ?43‰) of catagenetic origin is observed in the study area. Geo-microbial prospecting method and adsorbed soil gas and carbon isotope studies have shown good correlation with existing oil/gas fields of Mehsana. Microbial surveys can independently precede other geochemical and geophysical surveys to delineate area warm with hydrocarbons, and mapped microbiological anomalies may provide focus for locales of hydrocarbon accumulation in the Mehsana Block of Cambay Basin.     

Primary cracking of kerogens. Experimenting and modelling C1, C2–C5, C6–C15 and C15+ classes of hydrocarbons formed

Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C₁, C₂–C₅, C₆–C₁₅ and C₁₅₊). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.     

Carbon-13 exchange between CO2 and CH4 under geothermal conditions

On the basis of recently reported data on the kinetics of carbon-13 exchange between CO₂ and CH₄ at temperatures above 500°C, first order rate constants $\text{log k = 11.16?10,190/T}$ were derived allowing variations in Δ, the difference in the isotopic composition of coexisting CO₂ and CH₄, to be evaluated as a function of initial composition and cooling rate of the rising geothermal fluid. Observed Δ-values in geothermal discharges are likely to represent frozen in compositions attained after minimum residence times of 20 ka at 400°C or 10 Ma at 300°C. The carbon-13 contents of any biogenic gases are unlikely to have been affected by thermal re-equilibration at temperatures below 200°C. The chemical equilibrium involving CO₂ and CH₄ can be expected to proceed about a hundred times faster than isotopic equilibration.     

Solubility of pyromorphite Pb5(PO4)3Cl-mimetite Pb5(AsO4)3Cl solid solution series

Pyromorphite Pb₅(PO₄)₃Cl and mimetite Pb₅(AsO₄)₃Cl are isostructural minerals with apatite. Due to their high environmental stability, they have gained considerable attention as metals sequestration agents in water treatment and contaminated soil remediation. Pyromorphite and mimetite can form a continuous solid solution series in near-Earth surface environments. Precipitation of the end members and intermediate members of the series is likely to occur in the areas where the cost-effective in situ immobilization reclamation method, based on phosphate amendments, is applied. In contrast to the widely studied thermodynamic parameters of pyromorphite and mimetite, knowledge of the thermodynamics of their solid solutions is sparse. To supplement the data, a number of compounds from the pyromorphite-mimetite series were synthesized at room temperature using a method to simulate the conditions in the near-Earth surface environments. Afterwards, batch dissolution and dissolution-recrystallization experiments of seven synthesized precipitates were conducted at 25 °C, pH = 2 and in a 0.05 M KNO₃ background electrolyte. The experiments were carried out for a period of 6 (dissolution) and 14 (dissolution-recrystallization) months. A plateau in the [Pb] evolution patterns was used to determine equilibrium. All seven dissolutions were congruent, and the ionic activity products (IAP) of the minerals from the pyromorphite-mimetite solid solution series were calculated based on the dissolution reaction: . The IAPs for pyromorphite and mimetite exhibit a significant difference in values over three orders of magnitude between approximately 10⁻⁷⁹ for pyromorphite and approximately 10⁻⁷⁶ for mimetite. The series appeared to be ideal, and Lippmann and Roozboom diagrams were used for better understanding of its thermodynamics. The results indicated a strong tendency of pyromorphite to partition into the solid phase in the series, which explains some of the naturally observed phenomena. The improvement of the lattice stability of the mimetite due to isostructural phosphate substitutions in anionic sites was observed. The thermodynamic data reported in this study supplement existing databases used in geochemical modeling.     

Geochemical exploration for hydrocarbons in the soils of southeast of Krishna-Godavari Basin, Andhra Pradesh

Surface adsorbed gas surveys and geo-microbiological surveys are known techniques of petroleum exploration and aim towards risk reduction in exploration by way of identifying the areas warm with hydrocarbons and to establish intense exploration priorities amongst the identified warm areas. The present investigation aims to explore correlation between the adsorbed gas distribution pattern with the distribution of the counts of methane, ethane, propane and butane microbial oxidizers in the sub soil samples to establish the role of the latter in identifying the upward migration of hydrocarbons especially in the known petroliferous Krishna-Godavari Basin, India. A total of 135 soil samples were collected near oil and gas fields of Tatipaka, Pasarlapudi areas of Krishna Godavari Basin, Andhra Pradesh. The soil samples were collected from a depth of 2?C2.5 m. The samples collected, were analyzed for indicator hydrocarbon oxidizing bacteria, adsorbed light gaseous hydrocarbons and carbon isotopes (??¹³C_methane). The microbial prospecting studies showed the presence of high bacterial population for methane (3.94 × 10⁵ cfu/gm), ethane (3.85 × 10⁵ cfu/gm), propane (4.85 × 10⁵ cfu/gm) and butane oxidizing bacteria (3.63 × 10⁵ cfu/gm) in soil samples indicating microseepage of hydrocarbons. The light gaseous hydrocarbon analysis showed 83 ppb, 92 ppb, 134 ppb, 187 ppb and 316 ppb of C₁, C₂, C₃, nC₄ and nC₅, respectively, and the carbon isotopic composition of ??¹³C₁ of the samples ranged between ? 36.6 ?? to ?22.7?? (Pee Dee Belemnite) values, which presents convincing evidence that the adsorbed soil gases collected from these sediments are of thermogenic origin. Geo-microbial prospecting method and adsorbed soil gas and carbon isotope studies have shown good correlation with existing oil/ gas fields of K.G basin. Microbial surveys indicating microseepage of hydrocarbons can, therefore, independently precede other geochemical and geophysical surveys to delineate areas warm with hydrocarbons and mapped microbiological anomalies may provide focus for locales of hydrocarbon accumulation in the K.G basin.     

Application of light hydrocarbons (C4–C13) to oil/source rock correlations:: a study of the light hydrocarbon compositions of source rocks and test fluids from offshore Mid-Norway

Relatively little work has been published on the correlation between the light hydrocarbon distributions in reservoir fluids and their proposed source rocks [Philippi, G. T. (1981)]. The aim of our work was to study this relationship in detail for samples from Mid-Norway. The main source rocks offshore Mid-Norway are the marine shales of the Late Jurassic Spekk Formation and the coals and paralic shales of the Early Jurassic Åre Formation. Reliable light hydrocarbon (C₄–C₁₃) data for source rock samples were acquired by thermal extraction-GC of the source rocks. Of these, notably the hydrocarbons in the C₆–C₈ range (routinely measured in test fluids) were used to discriminate between the Spekk and Åre Formation samples. A total of twenty-six samples from the Spekk Formation and twenty-four samples from the Åre Formation at different maturity levels and facies were analyzed. In general, the two source rock types differ in their light hydrocarbon composition by the presence of relatively more aromatics and cyclohexanes in the Åre samples, while the Spekk samples are richer in cyclopentanes and acyclic hydrocarbons. We show that source rock facies is a more important indicator of light hydrocarbon composition than maturity variation. Differences in the chemical composition, which can be used to discriminate between the two source rocks, were supported by differences in the carbon isotope composition of individual components of the same fraction, as determined by GHM-IR-MS analysis of eleven samples. Further, the light hydrocarbon compositions of reservoir fluids (oils and condensates) were compared with those for the source rock(s). Sixty-six gas chromatograms of oils and condensates, representing most of the known petroleum accumulations in Mid-Norway, were collected. Of these, five oil samples were selected for detailed isotopic analysis of individual components (GC-IR-MS). When using a classification scheme based on data from sediment samples, data for the light hydrocarbon fraction of oils and condensates indicate that the Spekk Formation is the dominant source for most of the fields from Mid-Norway, with a significant contribution from the Åre Formation being detected principally in one field. Differences in the chemical composition of the C₆–C₈ fractions were supported by differences in the carbon isotope composition of individual components, which also discriminate between the oils. Although the classification diagrams used in this study are based on source rock data from Mid-Norway, the method can be applied to other areas, providing that the diagrams are calibrated with source rock data from the area of interest.     

Stable carbon isotope geochemistry of adsorbed alkane gases in near-surface soils of the Saurashtra Basin,India

The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C₁) = 3–518; ethane (C₂) = 0–430; propane (C₃) = 0–331; i-butane (iC₄) = 0–297; n-butane (nC₄) = 2–116; i-pentane (iC₅) = 0–31 and n-pentane (nC₅) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ¹³C₁; δ¹³C₂ and δ¹³C₃ compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ¹³C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.     

Actinide crystal-liquid partitioning for clinopyroxene and Ca3(PO4)2

Using fission and alpha track radiography techniques, we have measured partition coefficients (D) for the actinide elements Th, U and Pu between diopsidic clinopyroxene, whitlockite [β-Ca₃ (PO₄)₂] and silicate liquid at 20kbar. Equilibrium partitioning at the crystal-liquid interface is assumed, and corrections for actinide zoning have been applied to the measured D values. Reproducibility for both actinide and minor element D values is carefully examined as a criterion for crystal-liquid interface equilibrium. The data are mostly compatible with interface equilibrium except for experiments at high cooling rates ( ? 30 deg/hr). Partition coefficients for Th/U/Pu of about 0.002/0.002/0.06 are measured for clinopyroxene and 1.2/0.5/3.4 for whitlockite. At an oxygen fugacity of 10^?8.5, Pu is much more readily incorporated into the crystalline phases than is U or Th because of the importance of trivalent Pu. The D_Pu(cpx) is similar to D(cpx) of the light rare earths supporting the concept of Pu/(rare earth) dating.     

N2-CH4（CO2）混合气体在线标样制备及其拉曼定量因子测定

利用混合气体的标准样品对激光拉曼探针进行标定,可以快速准确地对包裹体中的无机及有机气相组分进行定量分析。而常用的商用钢瓶装混合气体标样,存在费用高、气体组成单一固定等缺点。本文设计了一套在线标样制备装置,提出一种在线配置不同浓度和压力条件下混合气体标样的方法。利用高纯度(纯度99.999%)的N2、CH4以及CO2钢瓶气,经过在线混合增压,在5 MPa和10 MPa条件下制备了N2摩尔分数为30%、50%和70%的N2-CH4以及N2-CO2混合气体在线标样。该方法制备的标样与70%N2+30%CO2的商用钢瓶气标样对比表明,CO2与N2的拉曼相对峰高以及相对峰面积值的误差在4%以内,具有较高的准确度和重现性。通过不同压力和浓度条件下CH4以及CO2的拉曼相对定量因子测定表明,气体的相对定量因子在5~10 MPa压力条件下与压力及组成无关。地质样品应用结果表明,本方法可以方便、灵活、准确地按任意比例将两瓶及两瓶以上纯气体钢瓶样品进行混合及增压,为激光拉曼标定、气体组成原位测量等提供了一种新的技术思路。