煤生烃动力学研究进展

化学反应动力学是评价煤的生烃过程和生烃特性行之有效的方法。目前,煤生烃动力学模型理论研究和标定得到了不断的深化,煤生烃动力学研究在认识煤源岩成烃规律方面也有长足发展,并在煤源岩评价中初见成效。但是在压力条件下,关于生烃动力学在煤源岩定量和动态评价方面的研究则报道较少。另外,对单体化合物形成动力学的研究还处于探索之中。这些研究将代表煤源岩生烃动力学领域未来发展的重要方向。     

不同方法对提取原煤中PAHs分布的影响

选取超声提取法和索氏提取法,对淮北煤田主采煤层新鲜煤样中多环芳烃进行提取,并利用气相色谱-质谱联用仪对提取液中的多环芳烃进行定量分析,研究了不同方法对提取原煤中(US-EPA)优先控制的多环芳烃种类、质量分数和分布的影响。结果表明,在本实验条件下索氏提取法在提取原煤中多环芳烃能力上优于超声提取法。     

饶阳凹陷马西地区古近系层序地层与隐蔽油气藏勘探

利用地震、测井、岩相等资料,对饶阳凹陷马西地区古近系进行了层序地层学研究,将其划分为3个二级层序和10个三级层序。层序Ⅷ、Ⅸ、Ⅹ为河流层序,可划分为基准面上升体系域和基准面下降体系域;层序Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ、Ⅵ和Ⅶ为湖泊层序,每个层序可划分为低位体系域、湖侵体系域和高位体系域。在层序地层研究的基础上,认为马西地区同沉积构造坡折带的存在控制了砂体的展布、烃源岩的发育以及油气的运聚,因而对该地区隐蔽油气藏的形成起控制作用。建立了隐蔽油气藏在不同体系域中的发育模式,并提出了下一步勘探的有利方向。     

Hydropyrolysis: A new technique for the analysis of macromolecular material in meteorites

The carbonaceous chondrite meteorites are fragments of asteroids that have remained relatively unprocessed since the formation of the Solar System 4.56 billion years ago. The major organic component in these meteorites is a macromolecular phase that is resistant to solvent extraction. The information contained within macromolecular material can be accessed by degradative techniques such as pyrolysis. Hydropyrolysis refers to pyrolysis assisted by high hydrogen gas pressures and a dispersed sulphided molybdenum catalyst. Hydropyrolysis of the Murchison macromolecular material successfully releases much greater quantities of hydrocarbons than traditional pyrolysis techniques (twofold greater than hydrous pyrolysis) including significant amounts of high molecular weight polyaromatic hydrocarbons (PAH) such as phenanthrene, carbazole, fluoranthene, pyrene, chrysene, perylene, benzoperylene and coronene units with varying degrees of alkylation. When hydropyrolysis products are collected using a silica trap immersed in liquid nitrogen, the technique enables the solubilisation and retention of compounds with a wide range of volatilities (i.e. benzene to coronene). This report describes the hydropyrolysis method and the information it can provide about meteorite macromolecular material constitution.     

Vertical transport of polycyclic aromatic hydrocarbons in different particle-size fractions of sandy soils

Vertical transport of selected polycyclic aromatic hydrocarbons (PAHs) in different particle-size fractions of sandy soils was investigated by simulation experiments in soil columns. Tested soil samples were fractionized into three particle-sizes including sand, coarse silt and fine silt (2,000–50, 50–20 and <20 μm). Rainfall simulations were conducted in artificially PAHs contaminated soil columns with 30 cm length and 5 cm diameter in 40 days. PAHs were extracted from soil samples and determined by high performance liquid chromatography (HPLC). Results showed that the residue level of PAHs in fine silt fraction reached 35.85 mg/kg, which was significantly higher than those in sand and coarse silt fraction (16.28 and 11.80 mg/kg, respectively), probably because PAHs in macroporous fractions were prone to volatilize or degrade compared with that in microporous fractions. Linear relationship between the residue levels of individual PAH (R _PAHs) and the value of partition coefficient (log K _oc) was regressed as R _PAHs = 1.55 × log K _oc − 5.86, R ² = 0.91, n = 9. These results indicated that vertical transport of the mixed PAHs in soils were controlled both by the nature of PAHs (i.e. log K _oc, molecular weight), soil particle size and soil organic contents, which could influence the transport of PAHs.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 3. Comparison of Modelled C2–C5 Hydrocarbons with Surface Measurements

In part 3 of this series of papers on a new 3-D global troposphericchemical transport model, using an Integrated Modelling System (IMS), anevaluation of the model performance in simulating global distributions andseasonal variations for volatile organic compounds (VOCs) in the atmosphere,is presented. Comparisons of model OH concentrations with previous modelstudies show consistent modelled OH levels from the subtropics tomidlatitudes, while more discrepancies occur over the tropical lowlatitudes, with IMS predicting the highest levels of OH. The close agreementbetween modelled OH concentrations over midlatitudes, where high surfaceNO_xand VOC concentrations are also found, is indicative of the strongphotochemical coupling between NO_x, VOCs and O₃ overthese latitudes. IMSOH concentrations in the Northern Hemisphere (NH) midlatitudes during summerare generally lower than available measurements, implying that models ingeneral are underestimating OH levels at this location and time of year.Substantial differences between model OH concentrations over low latitudesclearly highlight areas of uncertainty between models. IMS OH concentrationsare the highest in general of the models compared, one possible reason isthat biogenic emissions of species such as isoprene and monoterpenes arehighest in IMS, leading to higher O₃ levels and hence higher OH.Generally, the IMS VOC concentrations show a similar seasonality to themeasurements at most locations. In general though, IMS tends to underestimatethe NH wintertime VOC maximum and overestimate the NH summertime VOCminimum. Such an overestimate in summer could be due to IMSunderestimating OH levels, or an overestimation of VOC emissions or possiblya problem with model transport, all of these possibilities are explored.Except for n-pentane, the model underprediction of a VOC maximum during theNH winter month strongly suggests a missing emission mechanism in the modelor an underestimate of an existing one. It is very likely that there is alack of time varying emission sources in the model to account for theseasonal change in emission behaviour such as increasing energy usage (e.g.,electricity and gas), road transportation, engine performance, and otheranthropogenic factors which show strong seasonal characteristics. Theanomalous overprediction of wintertime n-pentane compared with its closesummertime prediction with the measurements suggest that emissions in thiscase may be too high.     

砂岩储层中原油微生物降解的模拟实验研究

模拟辽河冷东-雷家地区的砂砾岩储层条件，采用该地区的正常原油，在３０℃恒温和充氧下以及有营养元素的水溶液中，进行了原油喜氧微生物降解实验。实验表明，经微生物降解后，原油的化学组成发生了较大变化，饱和烃含量下降，沥青质、非烃含量上升；水溶液的ｐＨ值下降，并在其中检测出了有机酸，可见在微生物的代谢过程中，原油中的烃类分子被部分转化为水溶性含氧酸性产物。降解实验的油样与取自同一地区的两个重质原油饱和烃气相色谱图比较，两者在组成上极其相近，其结果说明辽河油田的重油成因，是原油遭受了喜氧微生物的降解。实验对微生物降解过程的动力学进行了初步研究。微生物对饱和烃馏分中不同化合物的降解序列为:短链正构烷烃、长链正构烷烃、异构烷烃、环状烷烃。但当各组分间的浓度发生较大变化时，降解序列会有所不同。     

Geochemistry of shallow sediments in Guaymas Basin, gulf of California: hydrothermal gas and oil migration and effects of mineralogy

Offset of prograde hydrothermal alterations by retrograde reactions is evident in sediments from a piston core (PC6, 8 m long) from the Guaymas Basin, Gulf of California. Geochemical and mineralogical analyses of sediments and pore fluids show superimposed geochemical signals that indicate currently active reactions are modifying previously formed secondary solids. Hydrothermal barite was formed in a previously active flow channel between 150 and 250 cm depth. Hydrothermal gypsum is presently dissolving at depths > 780 cm, below which hydrothermal fluid flow is channeled by a secondary dolomite layer. Thermal stress of organic matter generates hydrothermal gas and petroleum having wide ranges of compositions and maturities. A significant amount of hydrothermally generated oil has been transported laterally through a porous debris flow (approx. 240 cm subbottom), overwhelming the indigenous bituminous matter. Water soluble petroleum constituents have disseminated throughout the cored sediments. From 400 to 700 cm depth the immature organic matter continues to experience thermally-enhanced diagenesis, and an even higher thermal stress has occurred at the bottom of the core. Enhanced bacterial degradation of organic matter has led to depletion of pore water sulfate and enrichment of ammonium (NH₄⁺) in both pore fluid and sediment, resulting in formation of NH₄⁺ bearing secondary clay minerals at depths below 780 cm.     

Primary alteration—oxidation of marine algal organic matter from oil source rocks of the North Sea and Norwegian Arctic: new findings

The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C₁₂ + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %₀δ¹³C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.     

Accumulation of copper in the Permian Kupferschiefer: A result of post-depositional redox reactions

Within the Central European Zechstein Basin the Permian Kupferschiefer has been deposited under anoxic conditions. In most parts of the basin, the metal content does not exceed values commonly observed in black shales. However, in areas near to the Zechstein sea-shore which are simultaneously related to rift zones a significant base metal enrichment is observed. Organic geochemical analyses of the copper-mineralized sections in the Kupferschiefer from Southwest Poland show that significant changes in the composition of organic matter are associated with the metal enrichment processes. Porphyrins, commonly abundant constituents of the shale, have been decomposed by oxidizing fluids. Additionally, aliphatic hydrocarbons have been largely removed from the bitumen and alkylated aromatic systems were affected by side-chain degradation. This particular type of alteration is explained by ascending oxidizing solutions which transported high amounts of base metals from Lower Permian red beds into the Kupferschiefer horizon acting as a geochemical trap. The metal precipitation is suggested to be a result of thermochemical sulphide production with organic matter acting as hydrogen source. In areas such as the Lower Rhine Basin in the bottom section of the Kupferschiefer the base metals lead and zinc as well as barium have been accumulated from basinal Carboniferous formation waters. Copper enrichment is not observed because potential source rocks are missing in this area. However, the observed compositional changes of the organic matter do not point towards thermochemical redox processes.