Abiogenic Fischer–Tropsch synthesis of hydrocarbons in alkaline igneous rocks; fluid inclusion, textural and isotopic evidence from the Lovozero complex, N.W. Russia

A detailed fluid inclusion study has been carried out on the hydrocarbon-bearing fluids found in the peralkaline complex, Lovozero. Petrographic, microthermometric, laser Raman and bulk gas data are presented and discussed in context with previously published data from Lovozero and similar hydrocarbon-bearing alkaline complexes in order to further understand the processes which have generated these hydrocarbons. CH₄-dominated inclusions have been identified in all Lovozero samples. They occur predominantly as secondary inclusions trapped along cleavage planes and healed fractures together with rare H₂O-dominant inclusions. They are consistently observed in close association with either arfvedsonite crystals, partially replaced by aegirine, aegirine crystals or areas of zeolitization. The majority of inclusions consist of a low-density fluid with CH₄ homogenisation temperatures between −25 and −120 °C. Those in near-surface hand specimens contain CH₄+H₂ (up to 40 mol%)±higher hydrocarbons. However, inclusions in borehole samples contain CH₄+higher hydrocarbons±H₂ indicating that, at depth, higher hydrocarbons are more likely to form. Estimated entrapment temperatures and pressures for these inclusions are 350 °C and 0.2–0.7 kbar. A population of high-density, liquid, CH₄-dominant inclusions have also been recorded, mainly in the borehole samples, homogenising between −78 and −99 °C. These consist of pure CH₄, trapped between 1.2 and 2.1 kbar and may represent an early CH₄-bearing fluid overprinted by the low-density population. The microthermometric and laser Raman data are in agreement with bulk gas data, which have recorded significant concentrations of H₂ and higher hydrocarbons up to C₆H₁₂ in these samples. These data, combined with published isotopic data for the gases CH₄, C₂H₆, H₂, He and Ar indicate that these hydrocarbons have an abiogenic, crustal origin and were generated during postmagmatic, low temperature, alteration reactions of the mineral assemblage. This would suggest that these data favour a model for formation of hydrocarbons through Fischer–Tropsch type reactions involving an early CO₂-rich fluid and H₂ derived from alteration reactions. This is in contrast to the late-magmatic model suggested for the formation of hydrocarbons in the similar peralkaline intrusion, Ilímaussaq, at temperatures between 400 and 500 °C.     

内蒙古乌日尼图钨钼矿床成矿流体特征及地质意义

乌日尼图钨钼矿位于内蒙古苏尼特左旗境内,是近几年该区新发现的较大规模的钨钼矿床.钨钼矿体主要产于燕山期花岗岩体的内外接触带附近,以细脉状矿化类型为主.该矿床中的流体包裹体主要发育气液两相、富气相、富液相和纯液相包裹体等类型.包裹体均一温度为130.0~371.7 ℃(峰值为160.0~260.0 ℃),盐度为0.2%~15.9% NaCl eqv(峰值为0.2%~12.5% NaCl eqv),属于中低温、中低盐度钨钼矿床.激光拉曼和群体包裹体成分分析结果表明,流体体系气相成分以H₂O、CO₂为主,其次为N₂、O₂以及少量CO、CH₄、C₂H₂、C₂H₄和C₂H₆等; 液相成分以Ca2+、Na+、SO₄2-、Cl-为主,其次为K+、F-、NO₃-、Mg2+以及少量Br-和Li+.成矿流体为H₂O-NaCl-CO₂体系.流体包裹体氢氧同位素分析表明,成矿流体的δ18O_水的含量范围为-2.11%~-0.11%,δD_水的含量范围为-85%~-108%,成矿流体为岩浆水与大气降水的混合物.结合矿床地质和成矿流体特征,认为该矿床为与燕山期岩浆活动有关的中低温热液石英脉型钨钼矿床,成矿物质以深源为主.      

甲烷及其同系物δ13C值反序排列特征的数值模拟与非生物成因天然气藏探讨

本文采用数值模拟的方法对天然气中甲烷及其同系物的δ13C排序特征进行了研究,结果表明:两种具正序分布特征的生物成因天然气混合后可产生具反序分布特征的天然气.相应地,两种具反序分布特征的非生物成因天然气混合后也可产生具正序分布特征的天然气.对于前者而言,作为混合的两个端元天然气,它们必须具有不同的成因或来源,或它们是明显不同的演化阶段的产物.关于松辽盆地昌德气藏若干口天然气井甲、乙、丙、丁烷碳同位素排序特征的讨论表明,用两种生物成因天然气混合的观点很难解释这种反序排列.     

庙西凹陷严重生物降解原油序列中三环萜烷的异常分布成因初探

对渤海湾盆地一系列生物降解原油的色谱-质谱分析结果表明,庙西凹陷PL15-8D与PL9-4井四个严重生物降解原油三环萜烷系列分布较为异常,主要表现为以C₂₃为主峰的后峰型、C₂₀与C₂₃为主峰的微弱双峰型以及以C₂₀与C₂₄为主峰的双峰型分布模式。强烈的生物降解作用导致C₁₉~C₂₃三环萜烷优先于C₂₄₊三环萜烷被不同程度地侵蚀,是形成这一异常分布的根本原因。三环萜烷系列相对丰度与绝对浓度的变化规律表明,不同碳数三环萜烷的生物降解作用同时发生,但其降解速率有明显差别,即抗生物降解能力不同。三环萜烷系列化合物（除C₂₀三环萜烷以外）的抗生物降解能力具有随碳数增加而增强的趋势,而C₂₀三环萜烷抗降解能力似乎强于C₂₁~C₂₃三环萜烷。原油中未检测到脱甲基三环萜烷,表明三环萜烷的降解并非通过微生物的脱甲基化作用,推测其降解途径是微生物氧化三环萜烷C环支链末端的甲基,形成对应的羧酸化合物。四个原油样品甾烷、藿烷与三环萜烷被微生物严重侵蚀,不能用于油源对比研究,而三芳甾烷未受生物降解影响,可作为研究区严重生物降解原油油源对比的有效指标。     

辽河盆地烃类气体组分及同位素组成

辽河盆地是一新生代断陷盆地,盆地内天然气资源丰富,天然气成因复杂.本文通过对该盆地80个天然气样中烃类气体组分组成及同位素组成的分析研究,探讨了该盆地烃类气体的成因,为盆地天然气勘探提供了地球化学方面的信息.     

松辽盆地庆深气田天然气成因类型鉴别

通过对松辽盆地徐家围子烃源岩和原油热模拟实验、烷烃气碳同位素组成分析, 认为在高演化阶段单一热力作用可以引起重烃气(δ13C₂ > δ13C₃ > δ13C₄) 碳同位素组成倒转, 但CH₄与C₂H₆(δ13C₁ > δ13C₂) 却很难发生倒转.庆深气田天然气重甲烷碳同位素组成、烷烃气碳同位素完全倒转、高稀有气体同位素组成(R/Ra > 1.0), 说明该气田天然气来源具有多样性.利用R/Ra与CO₂/3He和R/Ra与CH₄/3He关系对庆深气田天然气成因类型进行识别, 认为该气田烷烃气中甲烷有部分为无机成因, 重烃气则为有机成因.该地区高地温梯度导致有机成因重烃气碳同位素组成发生倒转, 而CH₄与C₂H₆碳同位素组成倒转主要与重碳同位素的无机甲烷混入有关.      

四川乌斯河铅锌矿床成矿流体特征及TSR作用初探

四川乌斯河铅锌矿床是赋存于震旦系灯影组白云岩中的大型铅锌矿床.本次研究结合最新的野外地质现象发现该矿床除存在前人所强调的沉积成矿作用以外,热液成矿作用非常明显.对该矿床流体包裹体进行细致的岩相学、显微测温和激光拉曼研究,揭示成矿流体特征,并探讨成矿机制.研究结果显示该矿床包裹体类型较为单一,以气液两相为主,均一温度主要集中于120~260 ℃,平均盐度为10.0% NaCl eqv,压力为32~68 MPa,成矿流体为中-低温、中等盐度.激光拉曼测试显示包裹体气相成分含有CH₄、H₂S、C₂H₆、C₂H₂、N₂和NH₃,为多元共存的流体体系.在热驱动力下(120~260 ℃),流体混合作用提供了物质基础(SO₄2-)、催化剂(Mg2+)和还原剂(有机质、CH₄和H₂S)促使硫酸盐热化学还原反应(TSR)启动.TSR反应过程中流体pH发生变化,进一步促进了金属硫化物沉淀.      

天然气运移的气体组分的地球化学示踪

本文通过我国不同含油气盆地典型地区岩石酸解气、罐顶气和天然气中化学组分分析,结合天然气的形成和盆地的地质演化,研究了天然气运移时组分的变化。结果表明,天然气通过地层孔隙系统运移时,组分会发生明显分馏,表现在甲烷相对重烃、异构丁烷相对正构丁烷的优先迁移。酸解气、罐顶气和成藏天然气中C₁/C₂+、iC₄/nC₄及总烃/非烃等比值,是天然气运移示踪的有效指标。     

塔北隆起雅克拉油气田原油成因特征

针对雅克拉油气田多个含油气层位的原油,进行了一系列的地球化学测试分析,对雅克拉油气田原油的地球化学特征、成因特征进行了解剖。研究结果表明,雅克拉油气田深浅不同层位原油轻烃组成与轻烃单体烃碳同位素、类异戊二烯烷烃组成以及原油与馏分碳同位素组成具有明显的海相原油特征;深浅层原油三环萜烷、C₂₈甾烷、三芳甾烷和甲基三芳甾烷以及原油与馏分碳同位素组成皆具有典型上奥陶统来源油的特征,与寒武-下奥陶统来源油特征差异明显,暗示雅克拉油气田原油来源于上奥陶统烃源层。     

广西百色盆地州景矿第三系褐煤有机地球化学与煤岩学研究 Ⅳ．单化合物碳稳定同位素推断生物标志物起源

一个未成熟褐煤抽提物中，高等植物生源化合物的同位素值在全煤碳同位素组成（δ１３Ｃ值－２７．０‰）的±２‰范围内，表明相似成煤植物对这些化合物的贡献，或者其成煤植物经历过相似的生物合成分馏效应。所检测的萜烃类按同位素差异分为两组:二萜类（δ１３Ｃ值－２５．０±１．４‰）和倍半萜类（δ１３Ｃ值－２５．９±１．５‰）平均较全煤样富集１～２％。１３Ｃ，而奥利烷－乌散烷－羽扇烷型衍生物（δ１３Ｃ值－２９．０±０．８‰）平均比全煤样减少１～２‰１３Ｃ。Ｃ₁₅～Ｃ₃₅正烷烃δ１３Ｃ平均值－３２．４±０．６‰，据此表明Ｃ₁₇～Ｃ₂₂和Ｃ₂₂～Ｃ₃₃正烷烃的同位素值与上述平均值没有明显差异。与全煤样相比较，该煤样抽提物的藿烷衍生物１３Ｃ值则减少８～３４‰，标志在成煤过程中甲烷的细菌循环起着作用。     

藏北高原双湖地区中侏罗统海相油页岩生物标志化合物分布特征及其意义

重点报道了藏北双湖地区中侏罗统海相油页岩的生物标志化合物特征,首次在该层位油页岩中检出丰富的正烷烃、类异戊二烯烷烃、萜类化合物及甾类化合物。正烷烃图谱呈单峰形,nC₁₅、nC₁₆或nC₁₇为主峰碳,轻烃组份占有绝对优势,OEP值 0.93～ 1.0 1,无明显的奇偶碳数优势分布;Pr/Ph值为 0.77～ 1.5 9,在剖面序列中呈波动分布,显示弱植烷优势或姥鲛烷优势;藿烷以C₃₀ 占优势,萜烷相对丰度五环三萜烷 >三环萜烷 >四环萜烷;规则甾烷∑ (C₂₇+C₂₈) >∑C₂₉,∑C₂₇/∑C₂₉值为 0.79～ 1.2 0,在剖面序列中下部C₂₇甾烷略占优势,上部C₂₉甾烷略占优势,重排甾烷C₂₇/规则甾烷C₂₇值为 0.5 1～ 3.6 3,在剖面序列中具有显著的波动性,同时检出了少量孕甾烷和 4-甲基甾烷。有机质母质构成中,既有丰富的藻类等低等水生生物,可能还有一定比例陆生高等植物输入混合的特点。油页岩处于成熟阶段,整个油页岩剖面序列具有一致的热演化程度。剖面中部油页岩具有极高的原始生产力,氧化-还原条件也是控制油页岩TOC和沥青“A”含量在剖面垂向变化的重要因素.     

A reassessment of models for hydrocarbon generation in the Khibiny nepheline syenite complex, Kola Peninsula, Russia

Although hydrocarbon-bearing fluids have been known from the alkaline igneous rocks of the Khibiny intrusion for many years, their origin remains enigmatic. A recently proposed model of post-magmatic hydrocarbon (HC) generation through Fischer-Tropsch (FT) type reactions suggests the hydration of Fe-bearing phases and release of H₂ which reacts with magmatically derived CO₂ to form CH₄ and higher HCs. However, new petrographic, microthermometric, laser Raman, bulk gas and isotope data are presented and discussed in the context of previously published work in order to reassess models of HC generation. The gas phase is dominated by CH₄ with only minor proportions of higher hydrocarbons. No remnants of the proposed primary CO₂-rich fluid are found in the complex. The majority of the fluid inclusions are of secondary nature and trapped in healed microfractures. This indicates a high fluid flux after magma crystallisation. Entrapment conditions for fluid inclusions are 450–550 °C at 2.8–4.5 kbar. These temperatures are too high for hydrocarbon gas generation through the FT reaction. Chemical analyses of rims of Fe-rich phases suggest that they are not the result of alteration but instead represent changes in magma composition during crystallisation. Furthermore, there is no clear relationship between the presence of Fe-rich minerals and the abundance of fluid inclusion planes (FIPs) as reported elsewhere. δ¹³C values for methane range from − 22.4‰ to − 5.4‰, confirming a largely abiogenic origin for the gas. The presence of primary CH₄-dominated fluid inclusions and melt inclusions, which contain a methane-rich gas phase, indicates a magmatic origin of the HCs. An increase in methane content, together with a decrease in δ¹³C isotope values towards the intrusion margin suggests that magmatically derived abiogenic hydrocarbons may have mixed with biogenic hydrocarbons derived from the surrounding country rocks.     

一种解释高-过成熟烷烃气碳同位素系列倒转的新观点:芳香烃脱甲基作用

天然气成因机理复杂,鉴于在高-过成熟阶段烷烃气碳同位素系列倒转普遍存在,而高-过成熟阶段有机质中常富含芳环结构,利用芳香烃（甲苯）热裂解实验探讨高-过成熟阶段烷烃气碳同位素系列倒转成因.甲苯热裂解实验表明随着模拟温度的增加,烷烃气产率逐渐增大;模拟产物中H₂产率也随着模拟温度的增加而增加.甲苯裂解产物中δ13C₁、δ13C₂和δ13C₃分布区间分别为-31.8‰~-27.7‰,-31.0‰~-20.4‰和-31.0‰~-20.4‰.在甲苯热模拟实验450℃时,出现了烷烃气碳同位素系列的部分倒转（δ13C₁>δ13C₂ < δ13C₃）.发现无论是煤成气还是油型气,在高-过成熟阶段都会出现烷烃气碳同位素系列的倒转,结合本次模拟实验结果,认为芳香烃脱甲基作用可能是烷烃气高-过成熟阶段出现碳同位素系列倒转的一个重要原因.      

吐鲁番-哈密盆地台北凹天然气的地球化学特征及其来源

本文在论述新疆维吾尔自治区东部吐鲁番-哈密盆地台北凹陷天然气地质与地球化学特征的基础上,讨论了天然气的来源,对采自吐哈盆地十余个天然气样进行了气体组分和碳、氢、氦同位素分析。天然气甲烷含量为60.85～84.40%,干湿指数（C₁/C+₂）为1.57～6.37,属湿气.甲烷碳氢同位素组成(δ13C₁、δD)分别为-43.0～-49.4‰和-220～-281‰.乙烷的δ13C₂-20.1～-34 0‰,δD:-259～-257‰。丙烷的δ13C₃-21.3～-26.7‰,δD:-114～-203‰。丁烷的δ13C₄-22.2～-28.2‰,δD:-93～-116‰。天然气中氦的同位素组成（He/He）为（3.17～7.01）×10.目前主要产层属侏罗系,天然气一般与轻质油同藏,侏罗系中于酪根类型主要为Ⅲ型,R。值为0.4～1.0%。地质地球化学资料表明台北凹陷天然气与来自侏罗系的轻质油可能不完全同源,相当一部分天然气也许来自古生界。天然气中的氦为地壳来源的氦。     

Grain boundary migration of water and carbon dioxide during uplift of garnet-zone Alpine Schist, New Zealand

Abstract Deformed quartz veins in garnet-zone schist adjacent to the active Alpine Fault, New Zealand, have fluid inclusions trapped along quartz grain boundaries. Textures suggest that the inclusions formed in their present shapes during annealing of the deformed veins. Many of the inclusions are empty, but some contain carbon dioxide with densities that range from 0.16 to 0.80 g cm⁻³. No water, nitrogen or methane was detected. The inclusions are considerably more CO₂-rich than either the primary metamorphic fluid (<5% CO₂) or fluids trapped in fracture-related situations in the same, or related, rocks (<50% CO₂). Enrichment of CO₂ is inferred to have resulted from selective migration (wicking) of saline water from the inclusions along water-wet grain boundaries after cooling-induced immiscibility of a water-CO₂ mixture. Inclusion volumes changed after loss of water. Non-wetting CO₂ remained trapped in the inclusions until further percolation progressively removed CO₂ in solution. This mechanism of fluid migration dominated in ductile quartz-rich rocks near, but below, the brittle-ductile transition. At deeper levels, hydraulic fracturing is also an important mechanism for fluid migration, whereas at shallower levels advection through open fractures dominates the fluid flow regime.     

泥炭的热模拟研究──过渡带气形成机理探讨

本文对现代泥炭进行了低温长时间模拟实验研究,并探讨了过渡带气的形成机理。甘南泥炭气、液态烃产率高。液态烃由热解油和残余气仿沥青“Ａ”两部分组成,热解油中以Ｃ_５─Ｃ_１４较轻馏分为主,残余氯仿沥青“Ａ”则以非烃、沥青质为主。随热演化程度增高,烃类增加,非烃和沥青质急剧减少。模拟气体组成以非烃气体（ＣＯ_２等）为主,随温度升高,气态烃产率升高,烃类气体中以甲烷为主。２００℃～４００℃温度下产生的甲烷碳同位素δ１３Ｃ为－５３.８２～－３３.６６‰。研究表明低热演化阶段伴随腐殖物质的降解和干酪根的分子重排作用能产生甲烷同位素较轻的生物－热催化过渡带气。     

The organic geochemistry of ancient sediments—Part II

Several shales and oils ranging in age from 3 million to 2·7 billion years have been investigated for their hydrocarbon content using gas chromatography and mass spectrometry as primary analytical tools. From the Soudan Shale from Minnesota (2·7 × 10⁹yr) the C₁₈, C₁₉, C₂₀ and C₂₁ isoprenoid-alkanes were obtained. The Antrim shale from Michigan (about 265 × 10⁶ yr) yielded the C₁₆, C₁₈, C₁₉, C₂₀ and C₂₁ isoprenoids, as well as a C₁₆ iso-alkane and the C₁₈ and C₁₉ cyclohexyl n-alkanes. The San Joaquin Oil (30 × 10⁶ yr) and the Abbott Rock Oil (3 × 10⁶ yr) contained the C₁₆, C₁₈, C₁₉, C₂₀ and the C₁₈, C₁₉, C₂₀ and C₂₁ isoprenoids respectively. In addition, a series of iso-alkanes (C₁₆−C₁₈), anteiso-alkanes (C₁₆−C₁₈) and n-alkylcyclohexanes (C₁₆−C₁₉) as well as a C₂₁ isoprenoid were obtained from the Nonesuch Seep Oil (1 × 10⁹ yr). This analysis provides a comprehensive picture of the types of biogenic hydrocarbons found in oils and shales of widely differing ages, and in particular, the finding of isoprenoid alkanes in the Soudan Shale furnishes evidence for life processes at that period of geological time.     

美国南佛罗里达盆地Sunniland原油和油源岩中芳烃的地球化学

本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C₂₂-C₃₀范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C₃₁-C₃₅)和C₂₄、C₂₆四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟.     

湘西北地区下寒武统牛蹄塘组页岩有机地球化学与矿物组成特征

文章以湘西北地区下寒武统牛蹄塘组页岩为研究对象,分析其有机地球化学及无机矿物特征,重点对其烃源岩生物标志化合物特征进行分析。结果表明:该套页岩残余有机碳（TOC）含量高、氯仿沥青"A"含量低、生烃潜量"S₁+S₂"较小,镜质组反射率R_o在2.3%~3.19%之间,达到了过成熟阶段,以生成干气为主。分子生物标志化合物结果显示正构烷烃呈双峰型,碳数大于C₂₂的中-高碳数烃占优势;Pr/Ph平均值为0.31,植烷优势明显,指示强还原的海相沉积环境;萜烷丰度顺序为五环三萜烷>三环萜烷>四环萜烷,γ-环蜡烷与C₃₀霍烷的比值普遍大于0.3,指示其沉积母质以浮游生物及海洋性自养菌为主,含有部分藻类;Ts/（Ts+Tm）在0.35~0.38之间,与镜质组反射率对成熟度的检测结果相互印证;规则甾烷C₂₇ > C₂₉ > C₂₈,指示其母质来源以浅海生物来源为主,所有样品中均检测出孕甾烷、升孕甾烷、重排甾烷及4-甲基甾烷,表明其经历过微生物降解作用。全岩矿物组分分析显示该套页岩具备较好的开发物性条件和较强的吸附性能。综合以上分析结果,提出研究区牛蹄塘组页岩具备较好的页岩气成烃成藏的物质条件,并为该区深入开展页岩气勘探目标区优选奠定了很好的工作基础。      

新疆阿尔泰巴特巴克布拉克铁矿床成矿作用研究

巴特巴克布拉克铁矿床赋存于上志留-下泥盆统康布铁堡组变质火山-沉积岩系中, 近矿围岩为石榴子石矽卡岩、角闪斜长变粒岩和浅粒岩。矿体总体顺层分布, 呈似层状、透镜状及不规则状, 空间上与矽卡岩密切相关。流体包裹体研究表明, 矽卡岩阶段形成的石榴子石中发育纯气体包裹体、气体包裹体、液体包裹体、含子矿物包裹体及熔融包裹体; 退化蚀变阶段发育液体包裹体和少量气体包裹体; 石英-硫化物阶段主要发育液体包裹体、含液体CO₂的三相包裹体及少量纯气体包裹体、气体包裹体和含子矿物包裹体。矽卡岩阶段均一温度变化为217 ℃~499 ℃, 在255 ℃出现峰值, 盐度(NaCl_eq)变化为8.68%~22.65%; 退化蚀变阶段均一温度变化为181 ℃~432 ℃, 在225 ℃出现峰值, 盐度变化为12.85%~22.65%; 石英-硫化物阶段均一温度变化为140 ℃~482 ℃, 在155 ℃出现峰值, 盐度变化为0.18%~42.40%。石榴子石、石英和方解石的 δ¹⁸ O_SMOW 变化为1.8‰~7.1‰, δ¹⁸Ο_Η2Ο为 -4.79‰~4.57‰, δD_SMOW 为 -128‰~-84‰, 表明矽卡岩阶段成矿流体主要为岩浆水, 混合少量大气降水; 石英-硫化物阶段大气降水所占比例明显增加。方解石δ¹³ C_V-PDB 变化为 -3.2‰~-2.0‰, 表明流体中的碳来自深部或地幔。