乍得Bongor强反转裂谷盆地高酸值原油成因

乍得Bongor盆地是受中非剪切带影响发育起来的中、新生代陆内强反转裂谷盆地,反转和走滑构造是盆地最显著的构造特征。所发现的原油主要为中质油(重度为20°～34°API),其次为重质油(重度小于20°API),普遍高含沥青质、高含蜡、高酸值、低含硫。为了探讨高酸值原油的成因,作者选择了该盆地15个不同酸值的原油样品,尝试应用高分辨率质谱分析原油有机酸的组成。分析结果表明,高酸值原油的有机酸主要由环烷酸组成;环烷酸碳原子数分布范围较宽,且以一环、二环、三环环烷酸为主。生物降解作用是形成高酸值原油的主要原因,而构造反转造成盆地抬升,则加速了生物降解作用的发生。     

应用高分辨率质谱分析苏丹高酸值原油成因

苏丹Muglad和Melut盆地是苏丹乃至整个中、西非剪切带最富含油气的盆地,所发现的原油主要为中质油(重度为20°～34°API),其次为重质油(重度小于20°API),普遍高含沥青质、高含蜡、高酸值、低含硫。为了探讨高酸值原油的成因,选择了苏丹地区18个不同酸值的原油样品,尝试高分辨率质谱分析上述原油有机酸的组成。结果表明,高酸值原油的有机酸主要由环烷酸组成;环烷酸的平均相对分子质量随降解作用程度增加而增大,分子碳原子数分布范围变宽;环烷酸以一环、二环、三环环烷酸为主。生物降解作用是形成高酸值原油的主要原因。     

NATURE OF NAPHTHENIC ACIDS IN BAKU CRUDE OILS AS A FUNCTION OF THE DEPTH OF OCCURRENCE

The author analyzes data on the contents of naphthenic acid in crude oils. Characteristics and properties of naphthenic acids in oils of adjacent formations are compared. The final conclusion denies the existence of any general relationship between the content of naphthenic acids and the depth of occurrence of oils of the deposits of the Apsheron Peninsula. --Royer and Roger, Inc.     

Extractable and bound lipid components in a freshwater sediment

Lipids directly extracted by organic solvents from sediment of a small eutrophic lake (Crose Mere) comprise free hydrocarbons, alcohols, sterols and monocarboxylic acids together with an esterified component yielding additional amounts of alcohols, sterols and monocarboxylic acids on saponification. The carbon-number distributions of the free lipid compound classes indicate a major contribution from allochthonous sources whereas the distributions within compound classes released on saponification are attributable to autochthonous sources. The more advanced state of decomposition of terrestrial biota relative to aquatic biota and the composition of the source organisms are postulated to be factors leading to the differences in distribution of corresponding free and esterified lipid classes. Acid hydrolysis of solvent-extracted sediment liberates additional lipid constituents belonging to the above compound classes. Of these bound lipids, the n-alkanes and branched/cyclic alkanoic acids show a more significant bacterial contribution than do the corresponding components obtained by solvent extraction alone.     

Ions of Organic Carboxylic Acids (Formic,Acetic, and Oxalic) in the Snow Cover of Permafrost Landscapes of Boreal Eastern Siberia

The distribution of ions of organic carboxylic acids (formic, acetic, and oxalic) was investigated in the snowpack of permafrost landscapes of the boreal zone of Eastern Siberia. The contents of formate-, acetate-, and oxalate-ions were determined in permafrost landscapes of different zones of latitudinal and mountain- belt types. The maximum contents of organic carboxylic acid ions were observed in the snow cover of middle-taiga landscapes. The input rate of the ions into the snow cover of middle-taiga and mountain landscapes is controlled by altitudinal zonation and correlates with the total mass of plant organisms, which are the main source of organic carboxylic acids in the atmosphere. The obtained data suggest that organic carboxyl acid ions were supplied mainly by the atmosphere (74–90%), whereas the contribution of soil respiration was minor. The upward migration of organic carboxylic acid ions from the substrate to the snow cover depends on soil and snow temperature. Cooling of the soil surface below–5°C results in a considerable decrease in the migration of organic carboxylic acid ions from soil to snow.     

Nitrogen distribution as a function of radiocarbon age in Paleosol humic acids

Humic acids were extracted from six Paleosols (buried soils), ranging in radiocarbon ages from about 6000 to 29,000 yr. The N distribution (total N, amino acid-N, amino sugar-N, ammonia-N and “unknown” N) in each Paleosol humic acid was determined. After 6 M HCl hydrolysis, amino acid-N and ammonia-N decreased with increasing age but relative concentrations of “unknown” N increased. Aspartic acid, valine and serine were the most stable amino acids. Concentrations of amino sugars were very small, with concentrations of galactosamine exceeding those of glucosamine. The data showed that with increasing age, identifiable N components were converted to complex polymeric compounds whose identities still remain unknown. The different N-forms in HA's of geological times are valuable geochemical markers which provide useful information on the history of these soils.     

Compositional and source characterization of base progressively extracted humic acids using pyrolytic gas chromatography mass spectrometry

Cyclic base extraction is a commonly used method for the isolation of humic acids from soils and sediments. However, every extract may differ in chemical composition due to the complex nature of humic acids. To better understand the chemical composition of each extract, the heterogeneous property of humic acids and their speciation in environmental samples, eight fractions of humic acids were obtained in the present work by progressive base-extraction of Pahokee peat, and their chemical composition was characterized using two complementary pyrolytic techniques, namely conventional pyrolysis and methylation pyrolysis (TMAH) GC/MS. These quick and effective procedures provide an insight into the structure of macromolecules. The work shows that the lignin-derived aromatic compounds are major components of pyrolysates in both pyrolytic techniques, while aliphatic compounds originating from microorganisms and plants are minor components. Other compounds derived from proteins and carbohydrates at lower concentrations were also detected. Fatty acids were found in the pyrolysis without methylation, indicating their association with humic acid in a free state. These compounds are different from those formed during pyrolysis with in situ methylation, where fatty acids are generally believed to be the cleavage products of carboxylic groups bound to humic acids. A relative decreasing abundance of aromatic components and increasing abundance of aliphatic components in the pyrolysates as the peat was progressively extracted was also observed in this work, suggesting that the extraction of more hydrophobic aliphatics may be delayed in comparison to the aromatic components. Speciation and origin differences may also be important particularly considering that the contribution from lignin organic matter decreased with extraction number, as the contribution of microbial organic matter increased. The observed change in chemical composition with the extracted fractions indicates again that the humic acid distribution and their speciation are complex, and complete extractions are necessary to obtain a representative humic acid sample.     

Amino acid abundances and stereochemistry in hydrothermally altered sediments from the Juan de Fuca Ridge, northeastern Pacific Ocean.

The Juan de Fuca Ridge is a hydrothermally active, sediment covered, spreading ridge situated a few hundred kilometres off the west coast of North America in the northeastern Pacific Ocean. Sediments from seven sites drilled during the Ocean Drilling Program (ODP) Legs 139 and 168 were analyzed for total hydrolyzable amino acids (THAA), individual amino acid distributions, total organic C (TOC) and total N (TN) contents. The aim was to evaluate the effects of hydrothermal stress on the decomposition and transformation of sedimentary amino acids. Hydrolyzable amino acids account for up to 3.3% of the total organic C content and up to 12% of the total N content of the upper sediments. The total amounts of amino acids decrease significantly with depth in all drilled holes. This trend is particularly pronounced in holes with a thermal gradient of around 0.6 degrees C/m or higher. The most abundant amino acids in shallow sediments are glycine, alanine, lysine, glutamic acid, valine and histidine. The changes in amino acid distributions in low temperature holes are characterized by increased relative abundances of non-protein beta-alanine and gamma-aminobutyric acid. In high temperature holes the amino acid compositions are characterized by high abundances of glycine, alanine, serine, ornithine and histidine at depth. D/L ratios of samples with amino acid distributions similar to those found in acid hydrolysates of kerogen, indicate that racemization rates of amino acids bound by condensation reactions may be diminished.     

Aliphatic components of Victorian brown coal lithotypes

Victorian brown coal occurs in five major lithotypes distinguishable by colour index, petrography and bulk chemical analyses. The distributions of solvent extractable (free) and base hydrolysable (bound) n-alkanes, n-monocar?ylic acids, n-?,ω-dicar?ylic acids, n-ω-hydroxycar?ylic acids and n-alcohols were determined for samples of each of the five lithotypes (lithotype profile) and for seven samples of identical lithotype classification spanning a 100 m interval (depth profile) taken from a continuous bore core. The distributions of free molecular components in all classes are indicative of the predominant higher plant origin of this immature coal and provide strong support for the view that different lithotypes have derived from different, yet fairly specific paleobotanical communities. Despite an overall similarity in the distributions of aliphatic components from samples of identical lithotype classification, changes in the absolute concentrations and carbon preference indices (CPIs) of specific functional classes are observed in response to catagenetic influences even across the very small rank interval of the depth profile samples. Molecular distributions of bound components are similar to those of their free counterparts except that CPIs are generally lower and the relative contributions of lower molecular weight homologues (i.e. <C₂₂) are higher. Thedistributions of bound dicar?ylic acids and hydroxycar?ylic acids appear to reflect variations in the oxic/anoxic nature of the depositional paleoenvironments.     

松粉热解脂肪酸生物标志物的特征及其地球化学意义

现代松粉的温－压热模拟实验中，产出的轻质烃和氯仿抽提物芳烃馏份的GC－MS分析均检出大量偶数碳优势明显的脂肪酸类分子生物标志物，轻烃主要为C16，C18烷酸及其甲，乙酯，芳烃组分相对比较复杂，包括饱和脂肪酸（酯），不饱和脂肪酸（酯）和脂肪酸内酯，前者碳数分布为C15－，C30，C16，C18碳酸（酯）相对丰度占绝对优势为特征，后者碳数分布为C20-C30,以C26，C28和C30脂肪酸内酯为主，在250℃以下样品中检测出相对丰度较高的不饱和C18碳酸（酯），脂肪酸酯化合物在极低的温度条件下便可排出，并分别在200－300℃和300－400℃之间形成两次产出高峰；花粉内质体中的游离态脂肪酸及不饱和脂肪酸形成低温阶段的第一次高峰；花粉壁脂质结构中的脂肪酸及饱和脂肪酸在较高温度阶段形成第二次高峰，原样及低温样品以脂肪酸酯为主，250℃及其以上温度条件下因水解产生较多的脂肪酸，随温率继续升高，脂肪酸酯易发生脱羰反应而生成链烷烃。400℃以后因强烈降解脂肪酸酯含量大大降低，这与350－450℃之间奇数碳优势正构烷烃在轻质烃和饱和烃中的大量产出相吻合，研究表明，植物花粉是沉积有机质中饱和及不饱和C16，C18脂肪酸酯的重要母源之一。     

The Omolon pallasite: Chemical composition,mineralogy, and genetic implications

The chemical composition of mineral components of the Omolon pallasite was determined by neutron-activation. Six types of olivines were distinguished. Four types differ in the abundance of Co relative to Ni of CI chondrites. The fifth and sixth types were distinguished on the basis of REE distribution in them. Both last types are variably enriched in LREE relative to CI chondrites. In terms of Ca content relative to CI chondrite, these six types are subdivided into two groups: low-calcium and high-calcium. The difference in Ca contents can be caused by different cooling rate of the precursor of these olivines. The distribution pattern of siderophile elements in the pallasite metal indicates that a metallic phase experienced chemical transformations since the time of its formation. The analysis of chemical composition of accessory minerals showed that: (1) HREE are accumulated in tridymite; (2) troilite and daubreelite were formed under different temperature conditions; (3) magnetite is the mineral of the outer zone of melting crust. Four fragments with anomalous contents of lithophile elements were found in the pallasites and studied. The unusual chemical composition of phases and high degree of HREE fractionation in the fragments suggest their formation at high temperatures at the early stage of the Solar system evolution. It is assumed that the Omolon pallasite was formed as impact-brecciated mixture of the asteroid core (with composition close to IIIAB group of iron meteorites) and mantle olivine from incompletely differentiated parent body of chondrite composition.     

烃源岩生成有机酸过程的高分辨质谱研究

研究石油中有机酸的生成过程对研究储层改造、石油润湿性及页岩油可动性评价具有重要意义。在热压生烃模拟实验基础上,对Ⅲ型烃源岩不同演化阶段生成油中的非烃馏分进行了负离子电喷雾傅立叶变换离子回旋共振质谱分析,研究了烃源岩生成有机酸过程。对样品生成有机酸分析表明,在整个演化过程烃源岩都能生成有机酸,在低演化阶段主要生成脂肪酸,随演化程度的升高,脂肪酸丰度快速减少,芳环酸开始大量生成。随演化程度的增加,芳环上短链取代基发生断裂,并促进了有机酸的缩合,使得生成的有机酸缩合度逐渐提高,高碳数有机酸逐渐减少;烃源岩生成脂肪酸系列中存在偶奇优势,生成的C16、C18脂肪酸存在异常高丰度, C16、C18脂肪酸异常丰度现象可能是污染造成的,是否与烃源岩类型及成熟度有关尚需进一步研究。     

Naphthene-aromatic hydrocarbons in oils of different genesis

Naphthene-benzenes, naphthene-naphthalenes, and naphthene-phenantrenes have been extracted with methanol from mono-, bi-, and triarene fractions of oils of different genetic types from the West Siberian, Timan–Pechora, North Caucasian, and Pannonian (Serbia) oil-and-gas-bearing basins. The hydrocarbon composition and molecular-mass distribution (MMD) of naphthene-arenes have been determined by mass spectrometry. Naphthene-benzene and naphthene-naphthalene molecules contain one to six naphthenic cycles, whereas naphthene-phenantrene molecules contain one to three naphthenic rings. The number of carbon atoms in the alkyl groups of naphthene-benzenes, naphthene-naphthalenes, and naphthene-phenantrenes reaches 38, 20, and 19, respectively. Distinctive features of group compositions and MMD of naphthene-arenes have been revealed in oils generated by different organic matter.     

Organic geochemistry of Recent equatorial deltaic sediments

The organic matter of recent deltaic sediments cored in the Mahakam delta, East Kalimantan, has been studied before and after physical fractionation into sands >50 μm, silts 5–50 μm and clays <5 μm. Both the lipid and non-lipid components have been investigated.Weight, carbon and nitrogen fractionation budgets were used to define three types of samples, depending on coarse particle contributions to the total amount of organic matter: a = a first type with more than 50% of the O.M. in the coarse particles, high C/N ratios and O.M. content, b = an intermediary type with medium C/N ratios and O.M. content, each fraction having quite the same O.M. content, c = a third type with less than 5% of the whole O.M. in the sands and the lowest C/N ratios and O.M. content.Concerning the global organic characteristics of the fractions, a systematic increase of C/N ratios occurs when going from clays to sands; the finer the fraction is, the more nitrogenous the compounds are. This enrichment in nitrogen is related to a persistent high rate of hydrolysable material either for argillaceous organic matter-poor sediments or for the clay fractions of all types of samples. Conversely, the type (a) coarse sediments, in particular the sandy components were resistant to acid hydrolysis with burial.Concerning the geochemical markers signatures of granulometric fractions, the distribution patterns of n-alkanes and n-fatty acids are characterized by the predominance of high molecular weight compounds >C₂₂. Carbon preference index (CPI) values are higher in the sands and silts, reflecting their enrichment in continentally-derived vegetation debris. For type (c), the fractionation revealed markers of microbial activity within the clay fractions. For all types of samples, we observed an increase with burial of the n-alkane and n-fatty acid concentrations, particularly in the clay fractions, suggesting possibly a better preservation and/or affinity of lipids with the finest fractions.     

Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: When clay minerals lead to identical molecular signature

Different studies have already pointed out the influence of clays during the analysis of pure organic compounds (especially alkanols, alkanoic acids) as well as macromolecules (humic acids) by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS). Especially, the occurrence of clay minerals favors the generation of aromatic units such as alkylbenzenes and polycyclic aromatic hydrocarbons. So as to better identify the nature of the organic compounds which are sensitive to the presence of clays during flash pyrolysis, a humic acid mixed in variable proportions of a Na-homoionic clay was tested. The smectite/humic acid mixtures containing from 10% to 100% humic acid allowed us to identify the progressive disappearance or appearance of specific compounds after PyGC–MS.n-Alk-1-enes disappear when the clay proportion is higher than 67%. For higher contents of Na-smectite, n-alkanes become less and less abundant with a preferential consumption of high molecular weight n-alkanes, whereas the aromatic hydrocarbon proportion increases. Moreover, the distribution of each aromatic hydrocarbon family (alkylbenzenes and alkylnaphthalenes) has been investigated. The pyrogram of pure humic acid exhibits a specific distribution of alkylbenzenes and alkylnaphthalenes reflecting the structure of the organic macromolecule. With the increase in clay proportion, these distributions are modified and lead to other distributions with a preferential predominance of thermally stable isomers.Pyrograms of humic acid and undecanoic acid in the presence of 90% of Na-smectite are similar, especially concerning alkylbenzene and alkylnaphthalene distributions. Therefore, clays (Na-smectite in our experiments) in high proportion modify initial organic products by recombination reactions and lead to the generation of new compounds of very similar distribution, whatever the nature of the initial organic matter. Such results underline the very important catalytic properties of clay minerals on functionalized organic matter during flash pyrolysis.     

Fatty acids of bacterial origin in contemporary marine sediments

Contributions by bacteria to recent sediments have been recognized as one important source of input for the extractable lipids. It has, however, proved difficult so far to conclusively relate the components identified to the contributing bacteria. This fact is primarily related to the lack of information on both the lipid chemistry of marine bacteria, and of detailed structures of the sedimentary lipids. In this paper a study of the fatty acids from a tropical marine sediment selected because of its high biomass content is reported, and relationships between the sedimentary extracts of the surface layer to fatty acid components of bacteria cultured from the sediment sample are detailed. By selecting specific structural features, a group of fatty acids have been identified as valid markers for bacteria in this environment: these include iso- and anteiso-branched chain acids; 10-methylpalmitic acid; cyclopropyl 17:0 and 19:0 acids of which ▽19:0 (11,12) is unique to bacteria; cis-vaccenic acid; and the 15:1, 17:1 ω6 and ω8 isomers especially when these occur in pairs; iso Δ7–15: 1 and iso Δ9–17:1 are branched unsaturated acids apparently unique to bacteria. Trans-monoene fatty acids are likely to be a direct bacterial input, and the hydroxy acids identified are probably of bacterial cell wall origin. This study, whilst emphasizing the necessity for detailed structural information on fatty acids in order to use them validly as biological markers, considerably extends the range of fatty acids as markers of bacterial input to contemporary sediments.     

The lignin component of humic substances: Distribution among soil and sedimentary humic,fulvic, and base-insoluble fractions

Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.     

Amino acid composition of organic matter associated with carbonate and non-carbonate sediments

Amino acids comprise from 15 to 36% by weight of humic substances from carbonate and non-carbonate sediments. Humic and fulvic acids extracted from carbonate sediments are characterized by an amino acid composition consisting primarily of the acidic amino acids, aspartic and glutamic acid. Humic substances from non-carbonate sediments have a distinctly different amino acid composition consisting primarily of glycine and alanine. Amino acid analyses of various molecular weight fractions of fulvic acids extracted from carbonates show that lower molecular weight fractions have appreciably higher relative abundances of the acidic amino acids compared to higher molecular weight fractions. Based on typical values for carboxyl group content in humic substances, acidic amino acids may be a significant contributor of these functional groups. Carbonate surfaces appear to selectively adsorb aspartic acid-enriched organic matter while non-carbonates do not have this property.     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

Isotopic fractionation associated with biosynthesis of fatty acids by a marine bacterium under oxic and anoxic conditions

Shewanella putrefaciens (Strain MR-4), a gram negative facultative marine bacterium, was grown to stationary phase under both aerobic and anaerobic conditions using lactate as the sole carbon source. Aerobically-produced cells were slightly enriched in ¹³C (+1.5‰) relative to the lactate carbon source, whereas those from anaerobic growth were depleted in ¹³C (−2.2‰). The distribution of fatty acids produced under aerobic conditions was similar to that resulting from anaerobic growth, being dominated by C_16:1 ω7 and C_16:0 fatty acids with a lesser amount of the C_18:1 ω7 component. Low concentrations of saturated even numbered normal fatty acids in the C₁₄ to C₁₈ range, and iso-C_15:0 were synthesized under both conditions. Fatty acids from anaerobic cultures (average δ¹³C=−37.8‰) were considerably depleted in ¹³C relative to their aerobically-synthesized counterparts (−28.8‰). The distinct differences in isotopic composition of both whole cells and individual fatty acid components result from differences in assimilation pathways. Under aerobic conditions, the primary route of assimilation involves the pyruvate dehydrogenase enzyme complex which produces acetyl-CoA, the precursor to lipid synthesis. In contrast, under anaerobic conditions formate, and not acetate, is the central intermediate in carbon assimilation with the precursors to fatty acid synthesis being produced via the serine pathway. Anaerobically-produced bacterial fatty acids were depleted by up to 12‰ relative to the carbon source. Therefore, detection of isotopically depleted fatty acids in sediments may be falsely attributed to a terrestrial origin, when in fact they are the result of bacterial resynthesis.