塔里木盆地前陆区和台盆区天然气的地球化学特征及成因

通过对塔里木盆地天然气碳氢同位素分析,主要存在两种类型天然气,即油型气与煤型气。油型气烷烃气碳同位素组成较轻（δ13C2＜-28‰,δ13C3＜-25‰）,氢同位素组成偏重,成烃母质主要为海相沉积环境形成的寒武系—下奥陶统或中下奥陶统烃源岩,分布区域主要为台盆区;而煤型气烷烃气碳同位素组成较重（δ13C2＞-28‰,δ13C3＞-25‰）,氢同位素组成偏轻,成烃母质主要为陆相沉积环境形成的三叠系—侏罗系烃源岩,分布区域主要为前陆区。在塔里木盆地,烷烃气同位素组成局部倒转主要与烃源岩热演化程度差异有关;同时,在局部地区硫酸盐热还原（TSR）也可引起碳同位素组成的局部倒转。塔里木盆地天然气中3He/4He值偏高可能与残留在岩石中的少量深部气体混入气藏有关。     

不纯碳酸盐碳氧同位素组成的在线分析

利用 GV IsoPrime(R)Ⅱ型稳定同位素质谱仪测量不纯碳酸盐样品的碳氧同位素组成,这些样品是用国家碳酸盐碳氧同位素一级标准物质 GBW04406与去除了碳酸盐的沉积物混合配制而成的, CaCO3含量在 2%～ 90%之间.结果显示 ,δ 13C内部精度为 0.002‰～ 0.005‰ (1σ ),δ 18O内部精度为 0.003‰～ 0.009‰ (1σ ),与测量所得的纯 CaCO3国际国内标准物质结果的内部精度范围一致,且外部精度达到仪器的指标要求,同时 ,不同 CaCO3含量样品的δ 13C和δ 18O的测量值 (测量平均值:δ 13C =-10.932‰± 0.021‰,δ 18O=-12.483‰± 0.054‰; 1σ )也在误差允许范围之内与 GBW04406推荐值 (δ 13C=-10.85‰± 0.05‰, δ 18O =-12.40‰± 0.15‰ ; 1σ )一致.可见碳酸盐的含量并不影响其碳氧同位素组成的分析结果,所以在线分析不纯碳酸盐的碳氧同位素组成是可行的,在线分析不纯碳酸盐样品的碳氧同位素组成之前应先对样品中碳酸盐含量进行大致估计,根据碳酸盐含量高低来确定样品用量以达到最佳分析效果.     

氧化作用对气态烃组成和碳同位素组成的影响

通过加水模拟实验,揭示了气态烃在被矿物氧化过程中分子组成和碳同位素组成的变化.实验结果表明,随着反应时间的延长,气态烃、非烃 (H2、 CO2、 H2S)组成及碳同位素组成发生了明显且很有规律的变化.气态烃碳数越高,氧化速率越快,碳同位素变化 (增重 )越大.当氧化剂为赤铁矿或赤铁矿 硫酸镁时, CH4含量没有明显降低,δ 13C值增重 1‰～ 2‰; C2H6含量最后 (288h)降低了约 20%,δ 13C值增重约 3‰; C3H8含量最后降低了约 50%,δ 13C值增重约 5‰; Ic4h10含量在 72 h时即降低了约 80%,氧化速率远高于 Nc4h10.非烃 CO2的含量增加了 1.26～ 1.71倍.当氧化剂为硫酸镁时, CH4含量明显增高,最多时增加了 34.7%,δ 13C值增重约 8‰; C2H6含量在 72 h时降低了约 14%,在 144 h时降低了约 85%,δ 13C值增重约 24‰; C3H8含量在 72 h时降低了约 65%,在 144 h时降低了 98%以上; Ic4h10和 Nc4h10在 72 h时即降低了 90%以上.非烃 CO2含量最多增加了 1.86倍, H2S最多增加了 9.62倍.这些实验结果对认识天然气藏在矿物氧化过程中分子组成和碳同位素组成的变化具有重要意义.     

烟草叶中异构和反异构烷烃的成因及其光合作用C同位素分馏效应

烟草叶是目前惟一可以通过生物合成得到大量异构和反异构烷烃的植物,然而许多文献对化合物中甲基碳位和奇偶碳数的变化成因未提及.对其成因进行了文献追踪,并对温室不同生长条件(温度、CO2和光照)下培育的烟草叶中的长链正构烷烃、异构和反异构烷烃的单体稳定C同位素组成进行了分析,以期对烟草叶中特殊脂类化合物的生物化学合成同位素分馏效应进行探索研究.与正构烷烃和异构烷烃相比,反异构烷烃的δ13C值平均相对偏重2‰,证明反异构烷烃确实具有不同的合成前身物(2-甲基丁酰辅酶A).比起甲基基团,脱羧反应很可能使得乙酰辅酶A的羧基基团δ13C值偏轻.本研究中异构烷烃和正构烷烃δ13C值的相似性,说明乙酰辅酶A和前身物2-甲基丙酰辅酶A(C4-CoA)之间的C同位素组成很可能是相似的.用水量越多,烟草叶中异构、反异构烷烃和正构烷烃稳定C同位素组成越偏轻.与强光条件比,弱光条件下培育的烟草叶中正构烷烃的稳定C同位素组成偏轻约2.2‰,异构和反异构烷烃稳定C同位素组成也分别偏轻1.8‰和1.9‰.温度对烟草叶正构烷烃、异构烷烃和反异构烷烃的稳定C同位素组成影响甚小,与Farquhar(1980)有关植物体C同位素组成的报道相吻合.     

川东北飞仙关组鲕滩天然气地球化学特征与成因

四川盆地东北部下三叠统飞仙关组鲕滩气藏天然气烃类气体以甲烷为主,含量主要分布在75%～90%之间,C2 含量很少,为0%～0.15%,干燥系数为0.997 0～0.999 8,是典型的干气;非烃气体以H2S和CO2为主,含量分别为4.21%～16.24%和0.97%～10.41%.天然气δ13C1值为-29.0‰～-31.5‰,δ13C2值为-29.4‰～-32.4‰.多参数表明鲕滩气藏天然气是以腐泥型为主的高过成熟天然气.高含H2S的天然气分布区域与含石膏地层分布基本一致,这些H2S为飞仙关组气藏附近的石膏经热化学硫酸盐还原作用(TSR)而生成,CO2是其主要的副产物.在TSR过程中,C2 重烃气体比甲烷更容易与硫酸盐发生反应,也就是C2 重烃气体的消耗速率大于甲烷,从而导致发生TSR反应的天然气C2 含量低、H2S和CO2含量高.天然气δ13C1值与甲烷含量之间具有很好的负相关关系,而与天然气酸性系数[H2S/(H2S CnH2n 2)]具有正相关关系.根据同位素动力学的分馏效应,随着TSR的进行,烃类分子中的12C损耗速率大于13C,残留下来的烃类分子中则更加富集13C,也就是TSR反应使天然气碳同位素变重.     

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。     

白云鄂博碳酸岩墙碳氧同位素地球化学

对内蒙古白云鄂博 REE- Fe- Nb矿床周围碳酸岩墙中共存的方解石和白云石进行了 C和 O同位素分析。结果表明，方解石和白云石的δ 13C值变化范围一致，均为－ 3.5‰～－ 7.3‰，落在正常地幔δ 13C值范围 (－ 5‰± 2‰ )内；而它们的δ 18O值可分为两组，第Ⅰ 组为 9.5‰～ 18.0‰，第Ⅱ 组为 20.6‰～ 22.6‰，均远大于正常地幔δ 18O值范围 (5.7‰± 1.0‰ )。第Ⅰ 组低δ 18O值样品中共存白云石与方解石之间的 C和 O同位素分馏均为负值，因此处于热力学不平衡状态，指示它们自形成后受到过后期热液蚀变，与先前的岩石学观察一致。相反，第Ⅱ 组高δ 18O值样品中白云石与方解石之间的 C和 O同位素分馏均为正值，处于热力学平衡状态，指示它们自形成后未受到后期热液蚀变，因此可能沉淀于晚期低温高δ 18O值流体。第Ⅰ 组碳酸岩墙中白云石的 C和 O同位素组成不呈线性分布，指示碳酸岩浆并非由幔源碳酸盐与沉积碳酸盐混合形成。应用水-岩交换模型计算得到，第Ⅰ 组碳酸岩在侵位后经历了碳酸岩浆期后热液的不均一蚀变，蚀变温度约在 220～ 800℃之间，蚀变流体的 CO2/H2O比值较小 (1/500)，但水 /岩比值变化较大 (10～ 400)。由于低温下方解石与热液之间的碳氧同位素交换速率大于白云石，导致这部分碳酸     

白云鄂博富稀土元素碳酸岩墙的 碳和氧同位素特征

重点解剖了一条距白云鄂博超大型REE-Nb-Fe矿床东矿北东方向2 k m、切割白云鄂 博群H1及H3岩性段的细粒方解石碳酸岩岩墙的碳和氧同位素地球化学特征。结果表明,碳酸 岩的碳同位素组成变化范围较小(δ13C值为－6.6‰ ～ －4.6‰),与正常地幔碳δ 13C值－5±2‰一致;而氧同位素组成变化范围较大(δ18O值为11.9‰～17.7‰ ),显著高于地幔的δ18O值5.7±1.0‰,表明碳酸岩浆在结晶过程中或之后曾与 低 温热液流体发生了同位素交换。碳酸岩墙中白云石与方解石之间的碳和氧同位素分馏均小于 0‰,处于不平衡状态,说明该碳酸岩墙中的白云石与方解石并非同成因矿物,白云石可能 为次生成因的。     

烷烃碳同位素对页岩含气性的指示意义——以四川盆地及周缘龙马溪组为例

以四川盆地及周缘龙马溪组为例,分析了烷烃碳同位素平面分布特征以及倒转情况,定量研究了烷烃碳同位素值与热演化程度、埋藏深度及含气量之间的关系,并探讨了造成不同区块烷烃碳同位素倒转程度差异的主要原因。结果表明:(1)龙马溪组页岩气组分具有典型的干气特征:CH4含量介于95.32%～99.59%,平均为98.44%;C2H6含量较少,介于0.09%～0.74%,平均为0.52%;C3H8含量普遍很低。(2)烷烃碳同位素表现为自盆地边缘向盆地中心逐渐变轻的特征,δ13C1值介于-36.9‰～-26.7‰,平均为-30.27‰;δ13C2值介于-42.8‰～-31‰,平均为-34.9‰;δ13C3值介于-50.5‰～-33.1‰,平均为-37.28‰。(3)整体上,四川盆地及周缘龙马溪组页岩气烷烃碳同位素具有完全倒转(δ13C1δ13C2δ13C3)的特征,页岩气成藏过程中干酪根裂解气与滞留烃裂解气的混合可能是导致烷烃碳同位素发生倒转的主要原因。(4)同位素定量分馏模型显示滞留烃裂解气在页岩气中的占比多大于60%,指示两种裂解气混合比不同是造成烷烃碳同位素倒转程度差异的主要原因;整体上,随滞留烃裂解气含量的增多,δ13C2值减小,烷烃碳同位素倒转程度增大,页岩的含气量也逐渐增加。     

岩溶地区现代土壤与洞穴石笋中单甲基支链烷烃与烷基环己烷对比研究

利用GC-MS（气相色谱—质谱仪）,对采自湖北清江流域和尚洞洞顶的土壤样品与洞内石笋样品进行分析,发现土壤中存在的七个系列单甲基支链烷烃在所有的石笋样品中均可以找到,呈现相似的分布模式,石笋中七个系列支链烷烃有可能来自洞穴滴水携带的土壤中的支链烷烃,但是也不能排除石笋原地生长的微生物的贡献。烷基环己烷的分布在土壤与石笋中呈现了相似的分布模式,但是主峰碳数有所变化,高碳数部分与低碳数部分的相对含量也发生了变化。主要原因可能是微生物选择性降解的结果,也有可能是土壤与石笋中微生物种类分布差异所造成的。本次研究初步显示了相对封闭稳定的洞穴沉积物与上覆土壤层中生物标志化合物的异同。      

Geogenic and anthropogenic zinc in epiphytic and terricolous lichens in Finland

At 31 sites in Finland the Zn content was determined of the epiphytic lichen Hypogymnia physodes (L.) Nyl. growing on pine and birch, the terricolous lichen Cladina spp. in pine bark, and the inner part of birch bark. The anomalous contents of Zn in H. physodes on pine and Cladina spp. in soil appeared to be strongly related to sulphide ore deposits. Anthropogenic Zn correlated closely with S and Fe in H. physodes on pine and with Fe in Cladina spp. The binding of geogenic Zn was related to iron hydroxides, and was attributed to the different uptake mechanism of S in these lichens. Elevated values of Zn in H. physodes on birch were due to both geogenic and anthropogenic sources. Zinc in pine bark increased with the Zn content in H. physodes and reached a limiting value.     

Hydrogen and carbon in solid solution in oxides and silicates

The dissolution of H₂O and CO₂ in structurally dense, nominally anhydrous and non-carbonate oxide matrices such as MgO and CaO is reviewed. H₂O and CO₂ are treated as gaseous oxide components which enter into solid solution with the refractory oxide hosts. They form anion complexes associated with cation vacancy sites. Evidence is presented that OH^? pairs which derive from the dissolution of H₂O are subject to a charge transfer (CT) conversion into peroxy moieties and molecular hydrogen, O ₂ ^2? ... H₂. Because the O ₂ ^2? moiety is small (O^?-O^? distance ≈ 1.5 Å) high pressure probably favors the CT conversion. Mass spectroscopic studies show that molecular H₂ may be lost from the solid which retains excess oxygen in the form of O ₂ ^2? , leading to the release of atomic O. The dissociation of O ₂ ^2? moieties into a vacancy-bound O^? state and an unbound O^? state can be followed by measuring the internal redox reactions involving transition metal impurities, the transient paramagnetism of the O^? and their effect on the d.c. conductivity. Evidence is presented that CO₂ molecules dissolve dissociatively in the structurally dense oxide matrix, as if they were first to dissociate into CO+O and then to form separate solute moieties CO ₂ ^2? and O ₂ ^2? , both associated with cation vacancy sites. In the CO ₂ ^2? moiety (C-O^? distance 1.2–1.3 Å, OCO angle ≈ 130°) the C atom probably sits off center. The transition of the C atom into interstitial sites is accompanied by dissociation of the CO ₂ ^2? moiety into CO^? and O^?. This transition can be followed by infrared spectroscopy, using OH^? as local probes. Further support derives from magnetic susceptibility, thermal expansion, low frequency dielectric loss and low temperature deformation measurements. The recently observed emission of O and Mg atoms besides a variety of molecules such as CO, CO₂, CH₄, HCN and other hydrocarbons during impact fracture of MgO single crystals is presented and discussed in the light of the other experimental data.     

Comparative urbanization in Ghana and Kenya in time and space

There are few inter-African country urban analyses because of the continent’s enormous size and socioeconomic diversity, language barriers, and wide variations in national and regional urban research capacity. Nevertheless, comparative urban studies are critical in understanding contemporary African urbanization. In this comparative spatial and temporal analysis of Ghana and Kenya’s urbanization, we find that both countries are urbanizing rapidly and are faced with many common urban problems. Moreover, Ghana is more urbanized than Kenya and has a larger indigenous urban imprint and a more widely dispersed urban pattern. Besides their physiographic and population conditions, we trace these countries’ convergent and divergent urban trends to their shared but unique experiences of colonialism, nationalism and globalization.     

Temporal and spatial variations in water discharge and sediment load in the Alaknanda and Bhagirathi Rivers in Himalaya, India

The Alaknanda and Bhagirathi Rivers originate in the mountainous regions of the Himalayas (Garhwal) and result in high sediment yields causing flood hazards downstream of the Ganga River and high sediment flux to the Bay of Bengal. The rivers are perennial, since runoff in these rivers is controlled by both precipitation and glacial melt. In the present study, three locations in the upper reaches of the Ganga River were monitored for 1 yr (daily observations of, more than >1000 samples) for suspended sediment concentrations. In addition, more than one hundred samples were collected from various locations of the Alaknanda and Bhagirathi Rivers at different periods to observe spatial and temporal variations in river suspensions. Further, multi-annual data (up to 40 yrs) of water flow and sediment concentrations were used for inferring the variations in water flow and sediment loads on longer time scales. In most previous studies of Himalayan Rivers, there has been a general lack of long term water flow and sediment load data. In the present study, we carried out high frequency sampling, considered long term discharge data and based on these information, discussed the temporal and spatial variations in water discharge and sediment loads in the rivers in the Himalayan region. The results show that, >75% of annual sediment loads are transported during the monsoon season (June through September). The annual physical weathering rates in the Alaknanda and Bhagirathi River basins at Devprayag are estimated to be 863 tons km⁻² yr⁻¹ (3.25 mm yr⁻¹) and 907 tons km⁻² yr⁻¹ (3.42 mm yr⁻¹) respectively, which are far in excess of the global average of 156 tons km⁻² yr⁻¹ (0.58 mm yr⁻¹).     

Discovery of Cinnabar in Soils in Hg Anomalous Zones in City and Town Areas and Their Surroundings and Its Significance

As a result of systematic study on heavy minerals in soils at city and town areas and their surroundings,cinnabar was discovered for the first time in areas of Hg anomalies in China, and it was found that the distribution of cinnabar was basically coincident in scope with that of Hg anomalies, showing that Hg anomalies were‘closely related to cinnabar. This finding provides a theoretical basis for a verification of Hg anomalies in soils in city and town areas and their surroundings, as well as evaluation of its ecological effects, and is significant to revealing the occurrence modes and origin of Hg in soils.     

Regional gravity survey and application in oil and gas exploration in China

Ground gravity survey for regional structure unit delineation and oil and gas exploration in China is addressed in this paper with examples. Gravity survey scales, coverage, technical regulations and achievements at the national level are introduced, including data processing and anomaly interpretation techniques. Bouguer anomalies of terrestrial territories of China and classification of anomalous feature zones are also described; they are well correlated with lithotectonical boundaries, fault zones, and unexposed igneous plutons. Recent study results of petroliferous sedimentary basins are presented as well, including concealed boundaries and major structures of large basins. It is concluded that gravity survey is the most effective and economic method in unveiling unexposed and deep-seated structures, targeting and delineating oil and gas-bearing sedimentary basins, and locating main trap structures within prolific basins in early stage of exploration in China. Suggestions for improving exploration of both conventional and unconventional oil and gas reservoirs in China are also given in the paper.     

煤中气孔和镶嵌结构及其在煤变质研究中的意义

河南省禹县、新密和荥巩煤田山西组Ⅱ₁煤的贫煤和无烟煤中,气孔发育。气孔形态有椭圆状（图版1）、圆状及不规则状（图版2）,有的几个气孔连在一起呈大的朵状气孔(图版3)。此外,在荥巩煤田西部无烟煤中还发育有镀嵌结构(图版4)。      

Trends in Analytical Developments and Earth Science Applications in LA-ICP-MS and LA-MC-ICP-MS for 2004 and 2005

This review of laser ablation-inductively coupled plasma-mass spectrometry includes research that employed quadrupole instruments, and single-collector and multicollector magnetic sector field instruments. The most important trend in 2004–2005 was the growing appreciation that small matrix effects in LA-(MC)-ICP-MS need to be addressed in order to produce highly precise and accurate data by the method. The issue is most acute for isotope ratio measurements that require standard-sample-standard bracketing but can also be important for certain elemental analysis. Matrix-dependent elemental and isotopic fractionations were studied from the standpoint of laser-sample interactions and the behaviour of laser-generated particles in the ablation cell, transfer tubing and ICP torch. Innovations in LA-(MC)-ICP-MS involved signal smoothing, in torch laser ablation, on-line isotope dilution and molecular oxide monitoring. Other important research was carried out on the calibration and homogeneity of various reference materials; and the exploration of mature ( in situ U-Pb geochronology) and emerging (apatite fission-track chronometry, U-Th/He thermochronology, boron/strontium/uranium-series isotopic microanalysis) applications in the Earth sciences.     

俄罗斯油气钻采废弃物处理及其利用研究

生态安全和环境保护是世界各国都非常关心的问题。地质钻探和石油天然气钻采工作中产生大量废弃物,直接影响生态安全和环境保护,给经济建设和人民生活带来很大的负面影响。俄罗斯钻探工作者对此进行了研究,取得了一定效果。他们主要采用综合处理方法和磁化处理方法。利用这2种方法,废弃物不仅可以再生,而且还可以二次使用,有一定的创新和实际意义,值得引起我们的重视,建议对此进行研究与讨论。