含油气盆地油气同位素地球化学研究概述

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，幔源氮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，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。     

乍得Bongor盆地天然气地球化学特征及成因

Bongor盆地位于乍得境内的中非剪切带西北部,是中新生代重要的含油气盆地之一。笔者从Bongor盆地天然气组分组成及组分碳、氢同位素分析入手,综合运用常规有机地球化学分析方法,探讨了Bongor盆地不同构造单元天然气的成因及成熟度差异。分析认为,Bongor盆地天然气化学组成主要由烃类气体、非烃类气体和微量稀有气体组成,其中烃类气体属于生物热催化过渡带气、原油伴生气和凝析油伴生气等有机成因气,非烃气体主要包括无机成因的氮气、二氧化碳和氢气等。在天然气成因研究的基础上,笔者还开展了Bongor盆地烃类气体的组成及来源分析,包括气气对比和气源对比,研究认为,不同构造单元的烃类气体虽然组成相同,但相对含量略有差异,表明不同构造单元的天然气具有相似的母质来源：M组和P组的暗色泥页岩;但也不排除K组暗色泥页岩的生烃贡献。不同构造单元天然气烃类气体的成熟度差异较大,这是由于天然气源自不同层位烃源岩或同一层位烃源岩在不同演化阶段的生烃产物。     

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。     

祁连山冻土区天然气水合物分解气碳氢同位素组成特征

开展祁连山冻土区天然气水合物气体同位素研究,是解决其气体成因、来源等科学问题的一个重要手段。本研究采集祁连山南麓多年冻土区水合物科学钻探DK2和DK3孔共8个含水合物的岩芯样品,采用真空顶空法收集样品中水合物的分解气,分别用气相色谱(GC)、气相色谱同位素比值质谱(GC-IRMS)测定其气体成分和同位素组成,测试结果表明:祁连山冻土区天然气水合物样品的气体碳氢同位素变化较大,甲烷、乙烷和丙烷的碳同位素(δ13C)变化范围分别为-52.6‰～-48.1‰、-38.6‰～-30.7‰和-34.7‰～-21.2‰,而二氧化碳的碳同位素(δ13C)最低为-27.9‰,最高为16.7‰;甲烷、乙烷和丙烷的氢同位素(δD)变化范围分别为-285‰～-227‰、-276‰～-236‰和-247‰～-198‰。通过对这些碳氢同位素进行综合研究,包括气体分子组成与同位素的关系分析、甲烷的碳氢同位素之间的关系判断等,结果表明研究区天然气水合物的气体主要来源于热解气,而且是在淡水环境中形成的有机成因气。     

气相色谱-同位素比值质谱法测定天然气水合物气体单体碳氢同位素

天然气水合物气体同位素组成数据是其气体成因、运移与积聚过程研究的重要参数。目前天然气水合物气体单体碳、氢同位素仪器分析技术主要借鉴天然气的分析方法,但对水合物气的分解、收集、储存等前处理技术缺乏系统研究。本文利用气相色谱-同位素比值质谱(GC-IRMS)技术,对比研究了顶空法、注射器法和排水法等水合物气体分解与收集方法的实用性,以及铝塑气袋和丁基橡胶塞密封的玻璃顶空瓶对分解气的储存效果。实验结果表明:在丁基橡胶塞密封的玻璃顶空瓶内真空分解且原位储存是水合物气体单体碳、氢同位素分析的最佳前处理方法。方法标准偏差为0.12‰～0.23‰[δ13C-(C1-C3,CO2)]、1.0‰～1.8‰[δD-(C1-C3)];相对标准偏差(RSD,n=6)为0.38%～0.86%[δ13C-(C1-C3,CO2)]、0.62%～1.00%[δD-(C1-C3)]。通过对南海神狐海域、祁连山冻土区、人工合成水合物样品的分析测定,表明该方法简便实用、适用范围宽,可满足天然气水合物气体单体碳、氢同位素的分析要求。     

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。     

Carbon isotopes of Middle–Lower Jurassic coal-derived alkane gases from the major basins of northwestern China

Coal-derived hydrocarbons from Middle–Lower Jurassic coal-bearing strata in northwestern China are distributed in the Tarim, Junggar, Qaidam, and Turpan-Harmi basins. The former three basins are dominated by coal-derived gas fields, distributed in Cretaceous and Tertiary strata. Turpan-Harmi basin is characterized by coal-derived oil fields which occur in the coal measures. Based on analysis of gas components and carbon isotopic compositions from these basins, three conclusions are drawn in this contribution: 1) Alkane gases with reservoirs of coal measures have no carbon isotopic reversal, whereas alkane gases with reservoirs not of coal measures the extent of carbon isotopic reversal increases with increasing maturity; 2) Coal-derived alkane gases with high δ¹³C values are found in the Tarim and Qaidam basins (δ¹³C₁: − 19.0 to − 29.9‰; δ¹³C₂: − 18.8 to − 27.1‰), and those with lowest δ¹³C values occur in the Turpan-Harmi and Junggar basins (δ¹³C₁: − 40.1 to − 44.0‰; δ¹³C₂: − 24.7 to − 27.9‰); and 3) Individual specific carbon isotopic compositions of light hydrocarbons (C_5–8) in the coal-derived gases are lower than those in the oil-associated gases. The discovered carbon isotopic reversal of coal-derived gases is caused by isotopic fractionation during migration and secondary alteration. The high and low carbon isotopic values of coal-derived gases in China may have some significance on global natural gas research, especially the low carbon isotope value of methane may provide some information for early thermogenic gases. Coal-derived methane typically has much heavier δ¹³C than that of oil-associated methane, and this can be used for gas–source rock correlation. The heavy carbon isotope of coal-derived ethane is a common phenomenon in China and it shed lights on the discrimination of gas origin. Since most giant gas fields are of coal-derived origin, comparative studies on coal-derived and oil-associated gases have great significance on future natural gas exploration in the world.     

生物─热催化过渡带油气关系

本文在辽河盆地原油和天然气之间碳氢同位素关系研究的基础上，系统地研究了中国生物─热催化过渡带油气的地球化学特征，特别是它们之间同位素组成关系，划分出油气的不同组合类型，从而证明生物─热催化过渡带油气的自生自储特征，认为过渡带是油气形成聚集的重要垂向演化层段。同时为完善烃类形成的多源复合和多阶连续提供了佐证。     

天然气研究中的稀有气体地球化学应用模式

在对天然气稀有气体地球化学特征进行系统研究的基础上，建立了有关氦、氩同位素组成的横“人”字型的成因模式并提出两种成因类型:Ａ、壳－幔复合型；Ｂ、壳源型。同时，还论述了稀有气体的年代积累效应与气源对比，进行了大、中型气区天然气地球化学综合研究。     

川东北地区酸性气体中CO2成因与TSR作用影响

通过对川东北地区52个天然气样品化学组分和稳定碳同位素分析,天然气以烃类气体为主,且甲烷占绝对高含量,重烃气体甚微,干燥系数C1/C1+为0.989～1.0。非烃气体H2S和CO2含量变化较大,当二者含量大于5.0％时,具有较好的正相关性。川东北地区天然气中CO2主要包括碳酸盐岩热分解和TSR作用,其中碳酸盐岩热分解生成的CO2含量一般小于5.0％,13CCO2值小于-2‰,且CO2含量与13CCO2值具有正相关性;而TSR作用生成的CO2含量大于5.0％,13CCO2值多大于-2‰,且CO2含量与13CCO2值具有较弱的负相关性。CH4/CO2比值和（H2S+CO2）/（H2S+CO2+∑C1-3）比值能够较好地反映TSR作用程度;当CH4/CO2比值和（H2S+CO2）/（H2S+CO2+∑C1-3）比值分别小于10和大于0.1时,随着TSR作用增强,CH4/CO2比值减少,而（H2S+CO2）/（H2S+CO2+∑C1-3）比值呈指数增加。同时,遭受TSR作用改造的天然气具有较高CO2含量和重的13CCO2,造成13CCO2值与实验结果不一致性的可能原因是在TSR反应过程中部分CO2与硫酸盐中Mg2+、Fe2+和Ca2+等金属离子以碳酸盐的形式沉淀且残余的重碳同位素组成的CO2与酸性气体腐蚀碳酸盐储层形成的CO2相混合。     

Geochemical Characteristics and Genetic Types of Natural Gas in the Xinchang Gas Field, Sichuan Basin, SW China

The molecular compositions and stable carbon and hydrogen isotopic compositions of natural gas from the Xinchang gas field in the Sichuan Basin were investigated to determine the genetic types. The natural gas is mainly composed of methane (88.99%–98.01%), and the dryness coefficient varies between 0.908 and 0.997. The gas generally displays positive alkane carbon and hydrogen isotopic series. The geochemical characteristics and gas-source correlation indicate that the gases stored in the 5~(th) member of the Upper Triassic Xujiahe Formation are coal-type gases which are derived from source rocks in the stratum itself. The gases reservoired in the 4~(th) member of the Xujiahe Formation and Jurassic strata in the Xinchang gas field are also coal-type gases that are derived from source rocks in the 3~(rd) and 4~(th) members of the Xujiahe Formation. The gases reservoired in the 2~(nd) member of the Upper Triassic Xujiahe Formation are mainly coal-type gases with small amounts of oil-type gas that is derived from source rocks in the stratum itself. This is accompanied by a small amount of contribution brought by source rocks in the Upper Triassic Ma'antang and Xiaotangzi formations. The gases reservoired in the 4~(th) member of the Middle Triassic Leikoupo Formation are oil-type gases and are believed to be derived from the secondary cracking of oil which is most likely to be generated from the Upper Permian source rocks.     

Carbon isotopic composition and genetic types of natural gas in the Sichuan Basin,China

The origin and genetic types of natural gas in the Sichuan Basin are still disputed. To classify the origin and genetic types in different areas, the paper analyzes the carbon isotopic composition of gases and geologic features in the Sichuan Basin. The results showed that the gas sourced from terrestrial layers is typically characterized by terrestrial origin and was mainly accumulated nearby to form reservoir. The carbon isotopic composition of gas showed a normal combination sequence distribution, suggesting that natural gas in continental strata is not affected by secondary alteration or that this deformation is very weak. The gas source is singular, and only gas from the southern and northern Sichuan Basin shows the characteristic of mixed sources. However, marine gas presents the characteristics of an oil-formed gas. The carbon isotopic composition of natural gas in the western and central part of the basin mostly distributes in a normal combination sequence, and few of them showed an inversion, indicating that the gas perhaps had not experienced secondary alteration. The carbon isotopic composition of marine-origin gas in the southern, northern and eastern Sichuan Basin displays a completely different distribution pattern, which is probably caused by different mixing ratio of gas with multi-source and multi-period.     

松辽盆地庆深气田异常氢同位素组成成因研究

对松辽盆地徐家围子断陷庆深气田天然气组分、碳氢同位素和稀有气体同位素的分析表明,天然气以烷烃气为主,烷烃气碳同位素组成随着碳数增加呈变轻趋势,且δ13C1＆gt;-30‰, R/Ra一般大于1.0,δ13CCO2值介于-16.5‰~-5.1‰之间;氢同位素组成δD1=-205‰~-197‰,平均值为-203‰,δD2=-247‰~-160‰,平均值为-195‰,δD3=-237‰~-126‰,平均值为-163‰,且存在氢同位素组成倒转现象,即δD1＆gt;δD2＆lt;δD3。根据对庆深气田天然气不同地球化学特征分析,认为该气田烷烃气中重烃主要为有机成因,而 CH4有相当无机成因混入。庆深气田烷烃气氢同位素组成具有 CH4变化小,而重烃（δD2,δD3）变化大的特点。根据与朝阳沟地区天然气烷烃气氢同位素组成对比分析,认为 CH4主要表现为无机成因,而重烃气（δD2,δD3）主要为有机成因,且无机成因CH4氢同位素组成重于有机成因CH4。     

天然气中甲烷和CO_2的二元同位素特征

不同成因的天然气由于形成温度不同,往往会有不同的稳定同位素特征。但是,由于经常不能同时获得天然气以及它的生成母体的同位素成分,很难用单独的C或H同位素成分来确定它的形成温度。在形成天然气时,不同的温度会形成不同的二元同位素的浓度,温度越低,二元同位素的比例越大,因此只需要知道天然气本身的二元同位素的浓度,就可以确定形成温度,从而避免了需要知道天然气生成母体的同位素成分这一难题。本文利用高级量子化学计算,预测了不同温度下天然气中甲烷和CO2气体的二元同位素(Clumped isotope)的特征,提供用于天然气成因分析的新方法。     

Geochemical Characteristics of Natural Gases in the Sichuan Basin—A Further Discussion

This paper is the continuation of the paper published in 1985, with the emphasis on the irregular components of natural gases from the Sichuan Basin—the isotopic compositions of C,H and S, the n-and iso-alkane predominance (C₆-C₁₃) of methane homologues, the compositional characteristics of benzene and methylbenzene, and the distribution and geochemical characteristics of organic sulfur-bearing compounds including thiophen, thio-alcohol, etc. It is considered that natural gases from the Sichuan Basin have different distributional characteristics in different layers and locations, suggesting that they are controlled by a combination of factors such as kerogen type, maturity of organic matter and wall-rock assemblage.

1. The type of source material (or precursor) is a main factor affecting the geochemical characteristics of natural gases. T_3x-h and P₂l produce coal-series gases with type-III source material dominant. The C and H isotopic compositions of natural gases are heavier, the contents of C₆H₆ and C₇H₈ are high, C₇H₈/C₆H₆ < 1. the content of C₄H₄S is low, and the predominance in isoalkane (C₆C₁₃) is obvious. J₁t. P₁y. Z₂b. etc. produce oil-series gases with type-I and -II kerogens dominant, indicating that the geochemical characteristics of natural gases are different from those described above.
2. The maturity of organic matter is an important factor affecting the composition of natural gases.With increasing maturity of organic matter, the C and H isotopic compositions tend to become light. C₁ and C₂ isotopic values are nearly equal or even inverse, and C₄H₄S decreases in content.
3. Wall-rock assemblage has apparent influence on the S isotopic composition. The Middle-Lower Triassic series belongs to sulfate-carbonate formations enriched in gypsum. Therefore, the (δ³⁴S values of natural gases are relatively high (< 20 %.) against the lower values for other layers due to the absence of gypsum layers.

     

Gas genetic type and origin of hydrogen sulfide in the Zhongba gas field of the western Sichuan Basin, China

Natural gases and associated condensate oils from the Zhongba gas field in the western Sichuan Basin, China were investigated for gas genetic types and origin of H₂S by integrating gaseous and light hydrocarbon geochemistry, formation water compositions, S isotopes (δ³⁴S) and geological data. There are two types of natural gas accumulations in the studied area. Gases from the third member of the Middle Triassic Leikoupo Formation (T₂l³) are reservoired in a marine carbonate sequence and are characterized by high gas dryness, high H₂S and CO₂ contents, slightly heavy C isotopic values of CH₄ and widely variable C isotopic values of wet gases. They are highly mature thermogenic gases mainly derived from the Permian type II kerogens mixed with a small proportion of the Triassic coal-type gases. Gases from the second member of the Upper Triassic Xujiahe Formation (T₃x²) are reservoired in continental sandstones and characterized by low gas dryness, free of H₂S, slightly light C isotopic values of CH₄, and heavy and less variable C isotopic values of wet gases. They are coal-type gases derived from coal in the Triassic Xujiahe Formation.The H₂S from the Leikoupo Formation is most likely formed by thermochemical SO₄ reduction (TSR) even though other possibilities cannot be fully ruled out. The proposed TSR origin of H₂S is supported by geochemical compositions and geological interpretations. The reservoir in the Leikoupo Formation is dolomite dominated carbonate that contains gypsum and anhydrite. Petroleum compounds dissolved in water react with aqueous SO₄ species, which are derived from the dissolution of anhydrite. Burial history analysis reveals that from the temperature at which TSR occurred it was in the Late Jurassic to Early Cretaceous and TSR ceased due to uplift and cooling thereafter. TSR alteration is incomplete and mainly occurs in wet gas components as indicated by near constant CH₄ δ¹³C values, wide range variations of ethane, propane and butane δ¹³C values, and moderately high gas dryness. The δ³⁴S values in SO₄, elemental S and H₂S fall within the fractionation scope of TSR-derived H₂S. High organo-S compound concentrations together with the occurrence of 2-thiaadamantanes in the T₂l reservoir provide supplementary evidence for TSR related alteration.     

森林沼泽泥炭不同演化阶段气体碳氢同位素演化特征

煤层气的成因是石油地质学研究的热点.煤层气聚集存在着"累积聚气"和"阶段聚气"两种形式, 对于"阶段聚气" 的煤层气成因判识的地球化学研究还很薄弱.通过森林沼泽泥炭在不同温度下制备的样品进行热模拟实验, 首次获得了不同演化阶段甲烷、乙烷和二氧化碳的碳、氢同位素组成和演化规律.发现随着原始样品演化程度越高, 生成的甲烷和乙烷的碳、氢同位素组成具有变重的趋势; 同时, 甲烷和乙烷碳同位素组成明显地受原始样品演化程度的影响, 而氢同位素组成主要与成熟度密切相关.确定了成煤有机质在不同演化阶段生成的气体碳、氢同位素组成.首次获得了成煤有机质不同演化阶段热解气体碳、氢同位素组成与R_o之间的关系式.建立了甲烷与乙烷的碳、氢同位素之间的关系式, 形成了甲烷碳、氢同位素组成相关图.根据这些为研究不同成熟度区间生成的煤层气成因提供了科学数据, 为"阶段聚气"的煤层气地球化学特征认识及其成因判识提供了科学依据.并且, 将这些研究结果应用到我国沁水盆地南部煤层气研究, 认为该地区煤层气是在中侏罗世以后聚集而成, 具有"阶段聚气"的特征, 证明了热模拟研究成果对自然界煤层气成因的判识具有重要的科学意义.      

川东北元坝地区雷口坡组天然气来源与成藏分析

四川盆地雷口坡组已成为一个重要的天然气勘探目的层,有关雷口坡组天然气的来源以及雷口坡组是否具有生气潜力还存在争议。研究表明雷口坡组泥质白云岩与泥质灰岩有机碳含量平均达到0.72%,具有较高的生烃潜力。雷口坡组天然气以烃类气体为主,干燥系数为0.99。不同于其他海相层系天然气,其CO₂和N₂含量较少,总量<10%,仅含微量的H₂S;它们的甲烷碳同位素相对较重(-31.5‰~-36.3‰),而乙烷碳同位素较轻,基本上都小于-28‰(-27.7‰~-36.6‰),且部分气呈δ¹³C₁>δ¹³C₂反序分布,属高-过成熟海相油型气。其烷烃气系列碳同位素组成既不同于上覆的须家河组陆相天然气,也有异于下伏飞仙关组-长兴组海相气,具有不同的气源,经与雷口坡组烃源岩轻烃组成的对比,认为其气源主要来自本层位。成藏条件分析表明,雷口坡组天然气的富集主要受烃源岩和储层的发育及分布控制,只有紧邻烃源岩发育的浅滩相白云岩/裂缝型灰岩构成的“岩性圈闭”才能形成天然气的聚集。     

蜀南纳溪-合地区嘉陵江组天然气地球化学特征及其气源

通过分析纳溪—合江地区嘉陵江组天然气组分,碳、氢同位素组成以及该区烃源岩发育特征,认为嘉陵江组天然气为混源气,主要为下二叠统栖霞组—茅口组碳酸盐岩烃源岩生成的油型干气,混有下二叠统梁山组和上二叠统龙潭组生成的煤成气,下志留统龙马溪组泥质源岩可能也有贡献.研究区嘉陵江组烷烃气的氢同位素组成较重.纳溪气田烷烃气具有正常的碳...     

塔里木盆地哈拉哈塘凹陷天然气地球化学特征

哈拉哈塘凹陷位于塔里木盆地塔北隆起中部,具有良好的石油地质条件,是近期油气勘探的重点区带。天然气地球化学特征研究表明,该区天然气干燥系数较低,表现出典型湿气的特征,普遍含有微量的H2S;烷烃气δ13C1和δ13C2值分别为-50.5‰~-42.6‰和-40.2‰~-35.5‰,δD1值介于-262‰~-156‰之间,碳氢同位素系列表现出典型正序特征; C7轻烃组成具有正庚烷优势分布, C5~7轻烃组成以正构和异构烷烃为主。哈拉哈塘凹陷及周缘奥陶系天然气均为海相油型气,既有干酪根裂解气,也有原油裂解气,其中哈拉哈塘天然气中混入了相当比例的原油裂解初期形成的湿气,主要来自于南部阿满过渡带地区的中上奥陶统烃源岩,天然气中具有高δ13C值特征的CO2主要来自碳酸盐岩储层在酸性地层水作用下发生的溶蚀, H2S主要源自含硫化合物的热裂解。其中天然气发生的同位素部分倒转主要源自原油伴生气与原油裂解气的混合。