川中地区大安寨段分子标志物异常组合及其地球化学意义

在川中地区大安寨段烃源岩抽提物中检测出丰富的重排藿烷系列、重排补身烷系列、重排甾烷系列及C₂₆₊长链三环萜烷系列的分子标志物组合。结合烃源岩的有机质来源、沉积环境、热演化程度特征,探讨上述甾烷、萜烷分布特征指示的地质地球化学意义。结果表明：重排类化合物与C₂₆₊长链三环萜烷系列存在着某些相同的富集途径,重排藿烷系列富集途径多于重排补身烷系列、重排甾烷系列及C₂₆₊长链三环萜烷系列;特殊的甾烷、萜烷分布特征指示,烃源岩中有机质以湖泊内源(藻类和细菌等)为主,形成于范围局限的弱还原环境,高丰度的重排化合物指示,有机质热演化处于成熟阶段。此外,特殊的甾烷、萜烷分布特征还可能指示了特定的酸性粘土矿物、钙质沉积催化和形成环境中发育的特殊生物族群。综上,研究结果对分子标志物异常组合的地球化学应用具有重要的示范意义。     

塔里木盆地台盆区原油甾、萜烷浓度与热稳定性

对塔里木盆地台盆区未遭受生物降解的138个原油样品进行甾、萜烷定量分析,展示原油甾、萜烷浓度随成熟度变化特征。C23三环萜烷/(C23三环萜烷+C₃₀藿烷)值与甾、萜烷浓度图版显示各类甾、萜烷具有不同的热稳定性。依据热稳定性的差异将甾、萜烷分为3类:第1类包括Tm、C₂₉藿烷和C₃₀藿烷等五环三萜烷,随成熟度增高,这类化合物浓度降低较快,具有相对较低的热稳定性;第2类既包括Ts、C₂₉Ts和C₃₀重排藿烷等五环三萜烷,也包括C27和C₂₉规则甾烷各异构体,随成熟度增高,这类化合物浓度降低较慢,具有中等热稳定性;第3类包括C27重排甾烷、C21甾烷和C23三环萜烷,随成熟度增高,这类化合物浓度先增高、后降低,降低速率低于前2类化合物,表明其热稳定性相对较高。在常用的甾、萜烷成熟度指标中,Ts/(Ts+Tm)、C₂₉Ts/(C₂₉Ts+C₂₉藿烷)和C₃₀重排藿烷/(C     

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。     

松辽盆地梨树断陷原油高碳数三环萜烷分布特征及主控因素

对梨树断陷71个湖相原油样品的饱和烃和芳烃进行了气相色谱和色谱—质谱(GC-MS)分析,根据其生物标志化合物组合特征的差异将梨树断陷的原油划分为三种类型,不同成因类型的原油样品中三环萜烷的分布特征差异明显,其中Ⅰ类原油三环萜烷的浓度明显高于Ⅱ类原油,而Ⅱ类原油Σ三环萜烷/17α(H)-藿烷比值明显高于Ⅰ类原油,但不同类型原油中均存在较高含量的高碳数三环萜烷(C₂₈TT-C₂₉TT),其相对百分含量均高于低碳数三环萜烷(C₁₉TT-C₂₀TT、C₂₁TT、C₂₃TT)。从沉积环境、母质来源和成熟度三方面对高碳数三环萜烷的主控因素进行了探讨,结果表明,梨树断陷不同类型原油的母质来源都是以细菌及低等水生生物为主,(C₂₈TT-C₂₉TT)/17α(H)-藿烷与伽马蜡烷指数有一定的正相关性,说明偏还原性的咸水环境是高碳数三环萜烷富集的次要影响因素。就该研究区而言,Σ三环萜烷/17α(H)-藿烷比值与成熟度参数Ts/(Ts...     

水驱对原油饱和烃馏分影响的分子地球化学表征

利用GC、GC/MS分析技术,对水驱开发的曲9油藏进行了原油饱和烃馏分的动态变化对比。研究表明,随着水驱推进,在9个多月的动态监测中,原油饱和烃馏份表现出明显的变化规律,逐渐升高的有饱和烃相对含量、C₁₅-RD/C₁₅-D、C₁₅8β（H）-D/C₁₆8β（H）-HD、TTs/17α-H、RS/17α-H等比值;逐渐降低的有芳烃相对含量、轻重比参数∑nC_21-/∑nC₂₂₊、∑nC_14-/∑nC₁₅₊;基本保持稳定不变的有异构烷烃比值Pr/Ph、iC₁₈/Pr、iC₁₈/Ph,萜烷比值C₂₁/C₂₂TT、C₂₄/C₂₃TT、∑C_19-26/∑C_28-29TTs、C₃₀*/C₂₉Ts、C₃₅R/C₃₄R、Ol/C₃₀H、G/C₃₁R、C₃₁22S/（22S+22R）、C₃₀M/C₃₀H、Ts/（Ts+Tm）、C₂₉Ts/（C₂₉Ts+C₂₉H）,甾烷比值C₂₇-DS/C₂₇-RS、C₂₉20S/（20S+20R）、C₂₉ββ/（ββ+αα）、C₂₇-重排甾烷20S/（20S+20R）等;先升高再降低,或先降低再升高的分异变化的有Pr/nC₁₇和Ph/nC₁₈。水洗作用造成芳烃相对含量与轻重比的降低,生物降解作用引起了三环萜烷与规则甾烷相对藿烷的富集,二者虽然对相近碳数的异构烷烃、萜烷、甾烷比值影响甚微,却合力促使了补身烷参数的升高。注水过程中的色层效应进一步导致了饱和烃馏分的分异。     

黄骅坳陷齐家务地区的油源对比

黄骅坳陷齐家务地区储油层主要为下第三系沙河街组沙一下段白云质灰岩。该区原油具有高密度、高粘度、高含硫量、中低凝固点、高初馏点和高胶质和沥青质含量等物理性质。在地球化学特征上,高碳数正构烷烃具有明显的奇偶优势,类异戊二稀烷烃具有植烷优势,甾烷组成具有明显的C₂₇ααα甾烷优势,沙一段泥页岩的三环萜烷不发育、伽马蜡烷比较发育。这些地球化学特征表明该区原油为未熟-低熟油。分析原油和沙一段泥页岩的伽马蜡烷/C₃₀藿烷与C₂₉降藿烷/C₃₀藿烷的关系以及伽马蜡烷/C₃₀藿烷与Pr/Ph之间的关系,并结合地球化学特征,认为齐家务地区的烃源岩主要是沙一下段的泥页岩。     

热力作用对塔里木盆地海相原油中甾烷类化合物组成和分布的影响

为了探讨热力作用对原油中甾烷类化合物形成和分布的影响,对塔里木盆地26个典型海相原油样品和1个热模拟样品进行系统的地球化学研究。结果表明:不同演化阶段原油中甾烷类化合物组成和分布的变化较为明显。高熟阶段原油的热裂解作用导致了甾烷类化合物含量大幅降低,过熟阶段甾烷类化合物含量的短暂升高则与原油中高分子量的烃类化合物裂解有关。随着热演化程度的增加,C₂₇和C₂₉规则甾烷在生成和裂解速率上的不同,致使C₂₇/C₂₉规则甾烷的值呈现先减小后增大的趋势,所以C₂₇/C₂₉规则甾烷的值在成熟-高熟阶段不能用于物源方面评价。同样由于热稳定性差异的影响,原油C₂₉甾烷异构化参数在高熟阶段发生“倒转”,因此可利用甾烷异构化参数倒转的特征来判断原油的热演化阶段。而原油中重排甾烷/规则甾烷的值与成熟度具有较好的正相关性,可作为原油在成熟-高熟阶段有效的成熟度评价参数。     

鄂尔多斯盆地西南缘奥陶系泥页岩与碳酸盐岩生物标志物特征对比

通过采集鄂尔多斯盆地西南缘4个剖面奥陶系马家沟群碳酸盐岩和平凉组泥页岩样品,对其中可溶有机质饱和烃与芳烃组分进行GC-MS分析,对比研究了马家沟群碳酸盐岩和平凉组泥页岩生物标志化合物特征。结果表明,马家沟群与平凉组正构烷烃分布形式及峰型特征、生物标志化合物参数Pr/Ph、伽马蜡烷/C₃₀-αβ藿烷、C_20-29三环萜烷/(C_20-29三环萜烷+C_27-35藿烷),以及甲基菲指数(MPI)均存在明显差异,这些差异反映了其沉积环境与成熟度的不同,对于马家沟群与平凉组来源油的识别具有参考价值。马家沟群正构烷烃分布形式与甾/藿比值以及C₂₈/C₂₉ααα20R甾烷比值之间的对应关系,反映了母质输入的细微差别。Ts/(Ts+Tm)与伽马蜡烷/C₃₀-αβ藿烷比值之间的关系,C₂₉甾烷αββ/(αββ+ααα)比值变化与重排藿烷与重排甾烷丰度的关系,反映上述成熟度参数明显受沉积环境影响。     

茂名盆地羊角含矿区始新统油柑窝组油页岩有机地球化学特征及沉积环境

针对茂名盆地油页岩成矿机理问题,利用茂名盆地羊角含矿区始新统油柑窝组油页岩莱科（Leco）、热解、含油率以及生物标志化合物等分析,研究了其有机地球化学特征,讨论了油页岩有机质来源与沉积环境。结果表明：油柑窝组油页岩有机质丰度高,有机质类型为Ⅰ-Ⅱ₁型,含油率平均为5.98%,属品质中等偏好型;碳优势指数（I_CP）值（3.73~4.37）、奇偶优势（OEP）值（7.59~9.57）、较小甾烷C₂₉ααα20S/（20S+20R）、较低Ts/（Ts+Tm）以及最高热解峰温（T_max）值（428.00~434.00℃）均指示油柑窝组油页岩热演化处于未成熟阶段。正构烷烃气相色谱（GC）图显示为单峰式,主碳峰为C₂₇;∑C_21-/∑C₂₂₊与∑C₂₁₊₂₂/∑C₂₈₊₂₉均呈现低值,I_CP与OEP呈现高值,高碳数藿烷系列含量丰富,三环萜烷含量较低,未检测出奥利烷和羽扇烷等非藿类化合物,综合C₂₇-C₂₈-C₂₉规则甾烷相对含量特征,确定油柑窝组油页岩有机质来源主要为湖相藻类体以及细菌、浮游生物与陆生植物混合来源。总有机碳质量分数/全硫质量分数（TOC/S）值（41.14~170.08）、姥鲛烷/植烷（Pr/Ph）值（0.82~1.30）以及重排甾烷/规则甾烷值（0.06~1.10）指示油页岩沉积时水体为淡水、还原环境。在亚热带—温带温暖-湿润气候背景下,藻类等水生生物勃发引起的高湖泊生产力和淡水、还原环境是茂名盆地油柑窝组油页岩成矿的有利条件。     

柴达木盆地大柴旦盐湖现代沉积物中的生物标志化合物分布特征

大柴旦盐湖现代沉积中正构烷烃的分布具明显的奇偶优势。链状类异戌二烯型烷烃呈植烷优势。二环倍半萜烷中以补身烷和高补身烷为主。长键三环二萜系列中C₂₀三环二萜烷含量最高。甾烷中C₂₉甾烷高于C₂₇甾烷的含量。重排甾烷含量低而孕甾烷系列丰富。这是由盐湖相中特殊的生物构成和沉积环境所决定的。     

Gas-solid molecular structure differences

Molecular geometries for a variety of classes of compounds are discussed. Where available, the structures of free molecules are compared with those in the crystal. Information inferred about intermolecular interactions are augmented with observations on structural consequences of dimerization and complex formation. Examples include substituted benzenes, sulfones, siloxane derivatives, metal halides, group four dihalides, tetrahaloaluminates, and donor-acceptor complexes.     

The molecular composition of ambers

Bulk (elemental composition, IR, CP/MAS ¹³C NMR) and molecular (GC-MS) analyses have been performed on a series of ambers and resins derived from different locations (Dominican Republic, Philippines, Canada, Israel, New Zealand, Chile) having diverse botanical affinities (Araucariaceae, Hymenaea) and variable age (from Holocene to Early Cretaceous). No major differences have been observed from the elemental composition and the spectroscopic data; however, the molecular analyses of the solvent extractable fraction show that a specific mixture of components is present in each sample. These are mainly diterpenoid products that in general are also found abundantly in the higher plants from which the ambers and resins originate. Nevertheless, a direct relationship between major terpenoid constituents in fossil resins and precursor plant materials can only be established for the younger samples.Irrespective of the geographical or botanical origin of the ambers and resins, several common age-dependent molecular transformation trends can be recognized: (1) progressive loss of olefinic bonds (especially those located in exocyclic positions), (2) decrease of functionalized products, and (3) increasing proportion of aromatized components. However, even in the samples of older age (Cretaceous) the degree of aromatization is very low when compared with that of other higher-plant related materials such as fossilized woods or low rank coals. This indicates that maturation must involve essentially olefin polymerization processes instead of extensive aromatization.     

The origin of giant molecular clouds

The parameters of molecular clouds formed via the Parker instability with dominant radiative losses are estimated. In this scenario, the cloud parameters (such as their mean densities and masses) should depend on galactocentric radius. This dependence is determined mainly by radial variations of the gas metallicity and the flux of heating radiation in the Galaxy. Due to the development of the interchange mode of the Parker instability, the angular momentum of the clouds will not necessarily be parallel to the galactic rotation axis.     

Methanol and other molecular tracers of outflows and dense gas in the molecular cloud G345.01+1.79

The results of SEST millimeter observations of the molecular cloud G345.01+1.79 are presented. Spectra of CH₃OH, SO₂, SiO, HCO⁺, C¹⁸O, C³³S, C³⁴S, HCN, and DCN lines have been obtained. Mapping of the cloud in CH₃OH, SiO, and C³⁴S lines indicates that the maximum integrated intensity in the SiO and C³⁴S lines and in low-excitation CH₃OH transitions coincide with the northern group of methanol masers, while the corresponding maximum for high-excitation CH₃OH transitions coincides with the southern methanol-maser group. The physical parameters are estimated from the quasi-thermal CH₃OH lines under the large-velocity-gradient approximation, and their distribution on the sky derived. The density and temperature are higher toward the southern group of methanol masers than in the northern group. This may indicate that star formation is in an earlier stage of evolution in the northern than toward the southern group. A maser component can be distinguished in 14 (of 71) CH₃OH lines. We have detected for the first time weak, probably maser, emission in the CH₃OH lines at 148.11, 231.28, 165.05, 165.06, and 165.07 GHz. A blue wing is clearly visible in the CH₃OH, SiO, C¹⁸O, and SO₂ lines. The emission in this wing is probably associated with a compact source whose velocity is characteristic of the CH₃OH maser emission in the southern group of masers.     

Applications of molecular fossils in lacustrine stratigraphy

Biomarkers, or the so-called molecular fossils, are used tentatively in the Eogene lacustrine stratigraphy study in the Jiyang Sub-basin. Notwithstanding the fact that unidentified microfossils or amorphism and acritarchae are widely distributed in lacustrine source rocks, molecular fossils are useful to identify the sources. It is helpful to reconstruct the palaeo-enviroment, palaeo-ecosystem and compartmentalize the stratigraphic sequence by using molecular fossils with which the existence and types of microbes including bacteria, archaea and certain algae can be identified.     

Calculation of molecular weights of humic substances from colligative data: Application to aquatic humus and its molecular size fractions

A rigorous mathematical expression for the dependence of colligative properties on acid dissociation of water soluble humic substances is presented. New data for number average molecular weights of a river derived humic material and its gel permeation Chromatographic fractions are compared with $\text{M}\text{?}{}_{\mathrm{n}}$ values obtained by a reevaluation of previously published experimental observations on soil and water fulvic acids. The results reveal a remarkable similarity of fulvic acids from widely different sources with respect to number-average molecular weight.     

Gas-phase molecular structure and energetics of anionic silicates

The gas-phase stabilities of linear, branched and cyclic silicates made of up to five silicon atoms were studied with density functional theory (DFT). The starting geometries for the DFT calculations at the B3LYP/6-311+G(2d,2p) level of theory were obtained from classical molecular dynamics simulations. We have observed that geometric parameters and charges are mainly affected by the degree of deprotonation. Charges on Si atoms are also influenced by their degree of substitution. The enthalpy of deprotonation of the neutral species was found to decrease with the size of the molecule, while the average deprotonation enthalpy of highly charged compounds increased with molecular size. Furthermore, the formation of rings in highly charged silicates is enthalpically preferred to chain growth. These observations result from two competing effects: the easier distribution of negative charge in silicates with low charge density and the strong intramolecular repulsions present in silicates with high charge density. As a consequence, highly charged silicates in the gas phase tend to be as small and as highly condensed as possible, which is in line with experimental observations from solution NMR.     

Animated molecular dynamics simulations of hydrated caesium-smectite interlayers

Computer animation of center of mass coordinates obtained from 800 ps molecular dynamics simulations of Cs-smectite hydrates (1/3 and 2/3 water monolayers) provided information concerning the structure and dynamics of the interlayer region that could not be obtained through traditional simulation analysis methods. Cs⁺ formed inner sphere complexes with the mineral surface, and could be seen to jump from one attracting location near a layer charge site to the next, while water molecules were observed to migrate from the hydration shell of one ion to that of another. Neighboring ions maintained a partial hydration shell by sharing water molecules, such that a single water molecule hydrated two ions simultaneously for hundreds of picoseconds. Cs-montmorillonite hydrates featured the largest extent of this sharing interaction, because interlayer ions were able to inhabit positions near surface cavities as well as at their edges, close to oxygen triads. The greater positional freedom of Cs⁺ within the montmorillonite interlayer, a result of structural hydroxyl orientation and low tetrahedral charge, promoted the optimization of distances between cations and water molecules required for water sharing. Preference of Cs⁺ for locations near oxygen triads was observed within interlayer beidellite and hectorite. Water molecules also could be seen to interact directly with the mineral surface, entering its surface cavities to approach attracting charge sites and structural hydroxyls. With increasing water content, water molecules exhibited increased frequency and duration of both cavity habitation and water sharing interactions. Competition between Cs⁺ and water molecules for surface sites was evident. These important cooperative and competitive features of interlayer molecular behavior were uniquely revealed by animation of an otherwise highly complex simulation output.     

Masers in the cool molecular cloud L 379

We present the results of monitoring the H₂O masers in the IR sources IRAS 18265-1517 and IRAS 18277-1516 associated with the cool molecular cloud L 379, which contains high-velocity bipolar molecular jets. The sources were observed in the 1.35 cm H₂O line using the 22-m radio telescope of the Pushchino Radio Astronomy Observatory (Russia) during 1991–2004. We detected H₂O maser emission from IRAS 18265-1517 at radial velocities of 17.8 and 18.4 km/s, virtually coincident with the velocity of the molecular cloud derived from CO-line observations (18.4 km/s). The maser emission towards the other source, IRAS 18277-1516, was at higher velocities than the central velocity of the CO molecular cloud. The H₂O maser spots are most likely associated with a redshifted region of CO emission. Cyclic variability of the integrated H₂O maser emission that may be related to cyclic activity of the central star was detected for IRAS 18277-1516. The strongest and most long-lived component (V_LSR ≈ 20.6 km/s) displays a radial-velocity drift, which could be due to deceleration of a dense clump of matter (maser condensation) in the circumstellar medium during the descending branch of a strong flare. We found numerous emission features for both IRAS 18265-1517 and IRAS 18277-1516, providing evidence for fragmentation of the medium surrounding their central objects.     

Galaxies with anomalously high abundances of molecular hydrogen

A sample of 66 galaxies from the catalog of Bettoni et al. (CISM) with anomalously high molecular-to-atomic hydrogen mass ratios (M _mol/M _HI > 2) is analyzed. The sample galaxies do not differ systematically from the other galaxies in the catalog with the same morphological types, in terms of their photometric parameters, rotational velocities, dust contents, or the integrated masses of gas (for galaxies with the same linear sizes and disk angular momenta). This suggests that the overabundances of H₂ are due to the molecularization of HI. Galaxies with bars and active nuclei are found more frequently among galaxies with M _mol estimates in CISM. In a small fraction of cases, high M _mol/M _HI ratios are due to overestimation of M _mol due to overstimating of the conversion factor for the translation of CO-line intensities into the number of H₂ molecules along the line of sight. It is argued that the molecularization of the bulk of the gas mass could be due to the concentration of gas in the inner regions of the galactic disks and the resulting high gas pressures and relative low star-formation efficiencies, as is indeed observed in galaxies with high M _mol/M _HI ratios.