Geochemical significance of lipids and lipid-derived substructures interlaced in kerogen

Young kerogens isolated from seven freshwater lakes, six river mouths and four marine surface sediments were subjected to pyrolysis in vacuo. Their pyrolysates were trapped and separated subsequently for determination of hydrocarbons, fatty acids and alcohols. The abundances, carbon number distributions of long (C₁₂) polymethylene chain lipid compounds and relative abundances of pristenes are proposed as possible indices applicable to discrimination between young kerogens from freshwater lacustrine and marine sediments. Some oil-shale kerogens of Eocene and Permian age were pyrolyzed in the same way, where the chain-length distributions of the pyrolysis products showed similar trends as those observed for the pyrolysis of young kerogens.     

Conversion of sedimentary fatty acids from extractable (unbound + bound) to tightly bound form during mild heating

Prolonged heating (1–248 days) of a recent sediment was conducted under mild conditions (65 and 83°C) to understand the thermal behavior of extractable (unbound and bound) fatty acids (C_12C32). In the course of the heating, the concentrations of saturated and monounsaturated fatty acids first decreased, and then increased. This indicates that extractable fatty acids can be converted to a tightly bound form upon heating, before fatty acids are extensively released from sediment matrices. Changes in molecular distributions of extractable fatty acids upon heating were also observed. The higher molecular weight fatty acids (?C₂₀) are more likely to become tightly bound than are lower molecular weight (<C₂₀). Monounsaturated fatty acids (C_16:1 and C_18:1) are more easily converted to the tightly bound form than polyunsaturated fatty acids (C_18:2 and C_18:3). These differences probably reflect their mode of occurrence in sediments, which are closely related to their origin.     

Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.     

松辽盆地古龙页岩油储层干酪根的有机元素组成及其N元素的地球化学意义

对青山口组页岩的317件干酪根样品进行了工业、元素及能谱分析,对样品进行两次校正,引入合理评价干酪根C、H、O、N的指标Ccc、Hcc、Occ、Ncc概念。研究结果显示：古龙凹陷青山口组泥页岩Ⅰ型干酪根具有较高的Hcc、Ncc和很低的Occ,而Ⅲ型干酪根的Occ则较高,Hcc、Ncc较低。Ⅱ干酪根的Hcc和Ncc低于Ⅰ型干酪根,而高于Ⅲ型干酪根;Ⅱ干酪根的Occ高于Ⅰ型和Ⅲ型干酪根。Ncc主要以有机官能团（NH3+）方式存在的于黏土的F F纳缝中,而不是存在于黏土晶胞间的无机N（NH4）。微量元素研究表明,古龙青山口组页岩油储层沉积时经历了十几次干旱咸水环境,因为咸水环境有利于形成黏土的F F凝聚,使发育有NH3+官能团的有机质被吸附在黏土片的F F纳缝之间。随着深度的增加,Ncc的克分子量增加速率是Ccc克分子量增加速率的0. 96~2. 04倍,在青山口组1300~2550 m深度内青一段干酪根的Ncc含量明显比上部的干酪根相对高,主要原因与下部青一段藻类较富集有关,其次与Hcc的快速脱落而使Ncc相对富集有关,间接地揭示了青一段生烃能力较上部强。通过研究Ncc可以间接地知道古环境中的咸度、黏土的孔隙类型及其干酪根的来源。经过论证,Occ和Ncc越大,页岩的封存性也就越好,含油气性也越好。因此,Occ和Ncc值可以作为判别页岩油发育程度的指标。古龙页岩油储层的Ncc和Occ的研究可以提供一些重要的沉积环境、地球化学、黏土结构、干酪根有机质类型和成岩成储及成藏等信息,应该受到重视。     

Acid catalysis of alkyl hydrogen exchange and configurational isomerisation reactions: acyclic isoprenoid acids

Acid-catalysed alkyl hydrogen exchange and configurational isomerisation has been studied in a series of acyclic isoprenoid acids when they were heated at 160°C in the presence of a montmorillonite. Hydrogen exchange occurred between the adsorbed water of the clay surface and the a position of the isoprenoid acids. In cases where this position was chiral, exchange was accompanied by configurational isomerisation. Configurational isomerisation occurred more slowly in experiments conducted without a clay matrix in the presence of water. These results have been rationalized in terms of a reaction mechanism involving protonation of the carbonyl oxygen causing enolization and consequent hydrogen exchange at the a position of the acids. This mechanism was used to account for the relatively fast rate of isomerisation of C-2 chiral centres in sedimentary acyclic isoprenoid acids during maturation.     

东海表层沉积物黏土粒级中多态脂肪酸组成与地球化学特征

对东海陆架泥质沉积区两个代表性站位表层沉积物开展了黏土粒级分离提取,并对其依次进行溶剂萃取、碱解和酸解处理,得到结合程度不同的三种脂肪酸组分：有机溶剂抽提的游离态脂肪酸、碱解得到的碱解酸和酸解得到的酸解酸。三种赋存态酸的存在表明它们所联结的宏观分子的结构不同或所吸附黏土矿物的保护作用不同。不同赋存态酸的数量、组成和分布有一定差异,两站位相同赋存态酸的数量与组成也存在明显差异。组成与分布特征表明东海陆架泥质区超细颗粒物中脂肪酸以海洋内源藻类来源为主（〉70％）,陆源高等植物贡献相对较低,并有少量的细菌源贡献。各赋存态酸的降解程度为碱解酸高于酸解酸高于游离酸,可能与其在黏土中的赋存状态和吸附过程有关。靠近长江河口的表层沉积物样品（24站）海洋内源藻类贡献略低于远离河口的站位（30站）,陆源高等植物的输入稍高于后者,是受两泥质区沉积环境综合影响的结果。     

莺歌海盆地黏土矿物异常转化及其地质意义

莺歌海盆地因其异常高压和高温热流体强烈活动而孕育了多种特殊地质现象。应用分析化验资料与热力学计算相结合的方法,研究了莺歌海盆地黏土矿物转化的特征,分析了其成因。结果表明,莺歌海盆地发育三种黏土矿物转化类型:正常演化型、快速演化型和缓慢演化型。其中超压抑制黏土矿物转化,形成黏土矿物缓慢演化型;高温热流体活动促进黏土矿物转化,形成黏土矿物快速演化型。超压对黏土矿物转化的抑制作用延缓了H+、阳离子和层间水的排出,减弱了胶结作用和溶蚀作用,有利于在深部形成优质储层。热流体的活动加速了黏土矿物转化,增强了储层的胶结作用,不利于深部优质储层的发育。     

Kerogen-mineral reactions at raised temperatures in the presence of water

Kerogen has been artificially matured under “hydrous pyrolysis” conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330°C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry.In the 280°C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330°C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (40% wt/wt). Biomarker epimerisation reactions have also proceeded further in the 330°C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.     

生油岩矿物低温催化脂肪酸脱羧生烃的活性评价

在地质低温条件下,未熟生油岩矿物催化脂肪酸脱羧生烃反应生成的ＣＯ２含量很低,因此,通过金属镍催化剂将ＣＯ２转化为ＣＨ４后再用氢离子火焰检测器检测其含量,以提高检测的灵敏度。运用该方法评价了我国七个油田未熟生油岩矿物催化脂肪酸脱羧生烃活性实验结果表明,脂肪酸在未熟生油岩矿物低温催估作用下,其脱羧率与未熟生油岩矿物中的碳酸盐及过渡金属Ｆｅ元素的含量有关。     

泌阳凹陷地质流体对砂岩储集层中黏土矿物形成和分布的控制作用

运用扫描电镜观察和X射线衍射分析等技术,在对泌阳凹陷核桃园组砂岩储集层中黏土矿物分布特征研究的基础上,从黏土矿物的形成条件和形成过程入手,详细分析了地质流体的性质、组成、流动方式、迁移速度等对砂岩储集层中黏土矿物形成和分布的影响,指出砂岩储集层中参与成岩反应的碎屑活性组分和地质流体对砂岩储集层中黏土矿物的形成和分布具有控制作用,并讨论了它们的形成机理.研究表明,黏土矿物的形成和分布能够不同程度地影响砂岩储集层的孔渗性和含油气性;高岭石发育层段与次生孔隙的发育和渗透率的增加以及油气的富集层段具有良好的对应关系.     

苏北盆地金湖凹陷腰滩地区古近系阜宁组储层物性特征及其影响因素

苏北盆地金湖凹陷腰滩地区古近系阜宁组储层岩石类型以岩屑长石砂岩和长石砂岩为主,其成分成熟度中等,结构 成熟度中等到好。腰滩地区储层成岩作用主要包括压实、胶结、溶蚀和交代四种类型, 目前处于晚成岩阶段A期。研究区储 层的储集物性受成岩作用和构造运动的共同影响,主要表现为对孔隙度和渗透率的影响, 其中压实和胶结作用使储层原生 孔隙迅速减少、渗透率降低、储集物性变差,而溶解作用则是导致次生孔隙发育及改善砂岩储集性能的主要因素。压实作 用主要表现为刚性颗粒发生脆性破裂、塑性颗粒挤压变形或刚性颗粒嵌入塑性颗粒中、颗粒之间呈线接触和凹凸接触、碎 屑颗粒呈明显的定向排列等; 溶蚀作用表现为碳酸盐矿物的溶解; 胶结物主要为自生黏土矿物、碳酸盐和自生石英。交代作 用主要为碳酸盐胶结物交代石英、长石及岩屑颗粒及碳酸盐胶结物之间的相互交代等。构造运动使局部的储层物性得到改 善。     

南图尔盖盆地储层成岩作用及孔隙演化

储层储集性能普遍良好是南图尔盖盆地油气资源丰富的主要原因.通过对该盆地储层的岩石学特征、成岩作用及孔隙类型演化分析研究发现,砂岩的成岩作用及孔隙演化对储层的储集性能有着重要影响.在对大量薄片和岩心进行分析的基础上,运用扫描电镜和X衍射粘土分析等手段,对南图尔盖盆地砂岩储层研究结果表明,该区机械压实和压溶作用、杂基充填作用、胶结作用和交代作用使砂岩孔隙度降低,不稳定矿物的溶蚀作用导致储层次生孔隙发育.根据有机质的演化及粘土矿物的变化序列,成岩作用和孔隙演化随埋深具有明显的阶段性:早成岩阶段,孔隙类型以原生孔隙粒间孔为主;中成岩阶段,孔隙类型以原生、次生混合型为主;晚成岩阶段,孔隙类型以次生型为主.综合评价南图尔盖盆地储层发现,阿雷斯库姆组、阿克萨布拉克组和库姆科尔组为Ⅰ类储层,可作为今后油气勘探的主要目的层.     

超压背景下粘土矿物转化的化学动力学模型及应用

在目前的粘土矿物转化化学动力学模型中,人们仅考虑了温度、时间和流体介质的影响。然而新近的一些研究表明,超压可以抑制粘土矿物的转化,增加反应活化能。通过超压调节反应活化能,建立超压背景下粘土矿物转化的化学动力学模型,并根据渤海湾盆地板桥凹陷、歧北凹陷超压发育井和歧南凹陷超压不发育井的粘土矿物实测资料,确定了相关参数。模拟结果表明,在超压井中,伊/蒙混层中蒙皂石层含量S%的计算值与实测数据吻合较好,但与Pytter和Reynolds(1989)模型的预测结果相差甚远,在压力系数为1.2~1.7的地层中,超压对S%的抑制最大可达15%~20%。由于在蒙皂石向伊利石转化的过程中,释放出大量S i4+、Ca2+、Mg2+、Fe3+、Na+等阳离子,所以超压对粘土矿物转化的抑制,导致了泥岩中这些阳离子生成量的减少和相邻砂岩中许多胶结作用的延迟,这非常有利于深层(埋深>3 500 m)优质储层的发育和油气藏的形成。     

深部细粒碎屑岩储层成岩作用研究——以苏北盆地张家垛油田阜三段为例

毗邻烃源岩的细粒储层,由于其岩石结构、组分及沉积环境的特殊性,成岩作用表现出一定差异。本文以张家垛油田阜三段细粒碎屑岩储层为例,通过铸体薄片、X射线衍射、扫描电镜等相关分析,研究其成岩作用的特殊性。研究结果表明:(1)细粒储层的成分成熟度和结构成熟度较高,常被泥岩包裹,在压实作用中若存在欠压实,粒间孔可以被很好地保留下来;(2)细粒储层形成时水动力较弱,杂基含量高导致微孔较多;(3)大量的粘土矿物使孔隙比表面增加,抑制了后期硅质和碳酸盐胶结物的析出;(4)比表面的增加减缓了孔隙流体的对流速率和扩散速率,不利于次生孔隙的形成,粒度越细,次生孔隙越不发育。细粒碎屑岩储层有别于常规储层,对其特殊的成岩作用进行研究具有重要的理论价值和实际意义。     

Hydrous pyrolysis of New Albany and Phosphoria Shales: production kinetics of carboxylic acids and light hydrocarbons and interactions between the inorganic and organic chemical systems

Hydrous pyrolysis in flexible gold-bag autoclaves was used to study the production of carboxylic acids and light hydrocarbons from two marine type IIb source rocks (New Albany and Phosphoria Shales). Kerogen pyrolysis produced significant amounts of the monocarboxylic acids (acetic > propionic > butyric). The gases were dominated by CO₂ and methane, in that order, and progressively smaller amounts of the alkanes (ethane > propane > butane > pentane). Kinetic analyses of production rates for the New Albany Shale suggest mean activation energies (E) of 51-54 kcal/mol for both the light hydrocarbons and acids. Pressure had little effect on measured production rates for either shale over the pressure range investigated. Chemical thermodynamic speciation modeling suggests that in these experiments metal-organic acid anion complexation had little impact on aluminum speciation/solubility, but was important with respect to the alkaline earths.     

辽河三角洲大凌河河口湿地沉积物晚更新世以来的矿物特征及其物源、气候意义

对辽河三角洲大凌河河口湿地地区ZK3钻孔的58个沉积物样品中碎屑矿物和黏土矿物进行鉴定和分析,结果显示:碎屑矿物中轻矿物占比大,平均含量为95.7%,主要包括斜长石(43.89%)、钾长石(28.10%)和石英(22.45%);重矿物平均含量仅为4.3%,主要为普通角闪石(38.03%)、绿帘石(27.51%)和自生重晶石(12.01%)。黏土矿物中伊利石平均含量(50.3%)最高,其次为蒙脱石(24.5%)、绿泥石(12.7%)和高岭石(12.6%),黏土矿物组合为伊利石-蒙脱石-绿泥石-高岭石型。ZK3孔晚更新世以来沉积物的物源有所差异,但总体上来说,除河道和湖相沉积时期物源主要来自大凌河外,其它沉积环境中沉积物主要来自辽河和大辽河,物源相对稳定。黏土矿物组合特征所指示的气候变化过程与本区域的孢粉数据有很好的对应关系:45～31 ka BP处于庐山—大理的间冰期阶段,蒙脱石/(伊利石+绿泥石)比值较大,指示气候温和湿润;31～11 ka BP为大理冰期阶段,蒙脱石/高岭石比值较低,指示气候寒冷干燥;11 ka BP至今为冰后期阶段,随着新仙女木事件(YD)的结束,温度逐渐回升,蒙脱...     

Fatty acids and sterols of particulate matter in a brackish and seasonally anoxic coastal salt pond

Particulate matter and interfacial sediment from a seasonally anoxic coastal salt pond were analyzed for fatty acids and sterols to examine variations in organic sources, and compositional changes across the oxic-anoxic interface in the water column and at the sediment-water interface. Fatty acid distributions in suspended particles varied seasonally and as a function of depth. Fatty acids of algal origin (e.g. 16:3, 16:4, 18:3, 18:4) were abundant in particles in oxic surface waters, but these labile components were depleted in particles from the anoxic zone which instead were enriched in bacterial fatty acids (e.g. 16:1Δ⁹, 18:1Δ¹¹, anteiso-C₁₅). Sterol distributionsvaried less than fatty acid distributions and particles throughout the water column reflected an upper water algal source with little in situ alteration. There was evidence for an in situ conversion of Δ⁵-stenols to 5(α)H-stanols in suspended particles in the anoxic zone. Sinking particles and the interfacial sediment were compositionally similar to each other, but different from suspended particles. These data reflect differences in particle source, transport and transformation processes occuring in the water column.     

钱塘江下切河谷SE2孔全新世沉积物黏土矿物特征及其意义*

通过X射线衍射系统分析了杭州湾地区SE2孔全新世沉积物的黏土矿物组成,结果显示研究层段黏土矿物主要由伊利石、绿泥石、高岭石和蒙脱石组成;伊利石结晶度较好,化学风化指数普遍大于0.5,表明以化学风化为主,且风化趋势自下而上呈递减趋势。通过对比中国东南部主要河流沉积物的黏土矿物组成,认为钱塘江下切河谷全新世沉积物的黏土矿物组成具有较好的物源指示意义: 全新世 Ⅰ 段(即古河口湾和河漫滩)沉积物主要来自钱塘江上游,特征黏土矿物为高岭石,河口外物质贡献不大;Ⅱ 段(即现代河口湾和近岸浅海)沉积物包含较多蒙脱石,表明不仅包括钱塘江上游物质,河口外长江物质也开始进入钱塘江河口。黏土矿物中,高岭石对气候有较好的指示作用:中全新世高岭石含量达到最高值,反映气候最为湿热,化学风化程度最高;晚全新世含量逐渐降低,反映气候逐渐回冷,化学风化强度降低。     

钱塘江下切河谷SE2孔全新世沉积物黏土矿物特征及其意义*

通过X射线衍射系统分析了杭州湾地区SE2孔全新世沉积物的黏土矿物组成,结果显示研究层段黏土矿物主要由伊利石、绿泥石、高岭石和蒙脱石组成;伊利石结晶度较好,化学风化指数普遍大于0.5,表明以化学风化为主,且风化趋势自下而上呈递减趋势。通过对比中国东南部主要河流沉积物的黏土矿物组成,认为钱塘江下切河谷全新世沉积物的黏土矿物组成具有较好的物源指示意义: 全新世 Ⅰ 段(即古河口湾和河漫滩)沉积物主要来自钱塘江上游,特征黏土矿物为高岭石,河口外物质贡献不大;Ⅱ 段(即现代河口湾和近岸浅海)沉积物包含较多蒙脱石,表明不仅包括钱塘江上游物质,河口外长江物质也开始进入钱塘江河口。黏土矿物中,高岭石对气候有较好的指示作用:中全新世高岭石含量达到最高值,反映气候最为湿热,化学风化程度最高;晚全新世含量逐渐降低,反映气候逐渐回冷,化学风化强度降低。     

Oxygen-containing functional groups in land-derived humic acids—II. Changes in the oxygen distribution of humic acids during early diagenesis as revealed by derivatization methods

Extensive functional group analyses were performed on humic acids representative of eight increasing depth levels from a core drilled in the Mahakam delta (East Kalimantan, Indonesia). Oxygen amounts decrease observed during early diagenesis was related chiefly to loss of hydroxyl (lignol?) groups. Comparison between upper and deeper levels shows the following variations: hydroxyl group abundances go from 19 to 6% of humic oxygen. Identified functional groups amounts represent 47 to 32% of weight of moisture- and ash-free humic acids. No evidence of decarboxylation of humic material was detected.