利用自由基浓度研究盆地古地温的方法

主要讨论了利用自由基浓度研究盆地古地温的三种方法，并结合实测的自由基浓度值估算了塔里木盆地ＴＺ１井的古地温梯度和反演了琼东南盆地单井的热流变化历史．     

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.     

A quantitative study of the degradation of whale bone lipids: Implications for the preservation of fatty acids in marine sediments

The degradation and preservation affecting the biomarker record of ancient metazoa are not fully understood. We report on a five month experiment on the fate of fatty acids (FAs) during the degradation of recent whale vertebrae (Phocoena phocoena). Whale bones were analysed for extractable FAs and macromolecularly bound n-acyl compounds. Fresh bone showed extractable FAs dominated by 16:1ω7c, 16:0, 18:1ω9c and 18:0. Calculated degradation rate constant (k) values showed a rapid decrease in FA concentration, with k values higher for unsaturated than for saturated compounds (0.08/day for 18:1ω9c, 0.05/day for 16:0). The appearance or increased abundance of distinctive methyl branched (e.g. i/ai-15:0 and -17:0, 10Me-16:0) and hydroxy FAs (e.g. 10OH-16:0 and 10OH-18:0) were observed, providing clear evidence for the microbial degradation of bone organic matter and an input of lipids from specialised bacteria. Catalytic hydropyrolysis (HyPy) of demineralised extraction residues released up to 0.13% of the total n-C₁₆ and n-C₁₈ moieties in the degraded bones. This revealed that only a small, yet sizeable, portion of bone-derived fatty acyl units was sequestered into (proto)kerogen during the earliest stages of degradation.     

Mechanical properties of organic matter in shales mapped at the nanometer scale

The mechanical properties of organic matter strongly affect the way shales deform and fracture. However, the way organic matter responds to mechanical stresses is poorly understood, representing a critical obstacle to assessing oil and gas production in shale formations. Little is known about the mechanical properties of organic matter in fine grained rocks primarily because it often occupies tiny nanometer-scale voids between the mineral grains which cannot be accessed using standard mechanical testing techniques. Here, we use a new atomic force microscopy technique (PeakForce QNM™) to map the mechanical properties of organic and inorganic components at the nanometer scale. We find that the method is able to distinguish between different phases such as pyrite, quartz, clays, and organic matter. Moreover, within the organic component Young's modulus values ranged from 0 to 25 GPa; in 3 different samples – all of which come from thermally mature Type II/III source rocks in the dry gas window – a modal value of 15–16 GPa was measured, with additional peaks measured at ≤10 GPa. In addition, the maps suggest that some porous organic macerals possess a soft core surrounded by a harder outer shell 50–100 nm thick. Thus, our results demonstrate that the method represents a powerful new petrographic tool with which to characterize the mechanical properties of organic-rich sedimentary rocks.     

The indigenous origin of Witwatersrand “carbon”

In the Witwatersrand approximately 40% of the gold is intimately associated with so-called “carbon” in “carbon seam reefs”, which occur in over a dozen paleoplacers, many of them concentrated at two stratigraphic levels in the 7000-m-thick succession of Archean siliciclastic sedimentary rocks. This is reduced carbon, present as kerogen admixed in various proportions with derivative (now solid) bitumen(s). Oil generation and migration were active geological processes during Early Earth history. Numerous possible source rocks for oil generation, including the carbon seams themselves, occur within the Witwatersrand basin. In the Witwatersrand ore, oil-bearing fluid inclusions are also present, derived like the bitumen, by thermal maturation of the kerogen. The presence of kerogen and bitumen in the Witwatersrand sedimentary rocks, together with a wealth of observations on the spatial distribution of the carbon seams confirm that the carbon originated in situ from living organisms in microbial mat cover, as opposed to flowing in from elsewhere as liquid hydrocarbons as some researchers have suggested. Paleochannels, which truncated auriferous carbon seams early in the depositional history, are of widespread occurrence, and micro-synsedimentary faults offset carbon seams. The carbon seams are thus indigenous biogenic markers that grew contemporaneously with placer development. The various features highlighting the nature and spatial distribution of Witwatersrand carbon seams provide a classic case where field evidence trumps laboratory data in the reconstruction of geological processes.     

Geochemistry,Petrography and Spectroscopy of Organic Matter of Clay‐Associated Kerogen of Ypresian Series: Gafsa‐Metlaoui Phosphatic Basin,Tunisia

This work presents geochemical characterization of isolated kerogen out of clay fraction using petrography studies, infrared absorption and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, with N‐alkane distributions of saturated hydrocarbon. Mineralogical study of clay mineral associations was carried out using X‐ray diffraction (XRD), on Ypresian phosphatic series from Gafsa‐Metlaoui basin, Tunisia. The XRD data indicate that smectite, palygorskite and sepiolite are the prevalent clay minerals in the selected samples. In this clay mineral association, the N‐alkane (m/z = 57) distribution indicates that the marine organic matter is plankton and bacterial in origin. The kerogens observed on transmitted light microscopy, however, appear to be totally amorphous organic matter, without any appearance of biological form. The orange gel‐like amorphous organic matter with distinct edges and homogenous texture is consistent with a high degree of aliphaticity. This material has relatively intense CH₂ and CH₃ infrared bands in ¹³C NMR peaks. This aliphatic character is related to bacterial origin. Brown amorphous organic matter with diffuse edges has a lower aliphatic character than the previous kerogen, deduced from relatively low CH₂ and CH₃ infrared and ¹³C NMR band intensities.     

Hydrocarbon potential of the middle Eocene-middle Miocene Mesohellenic piggy-back basin (central Greece): A case study

Two depocentres, >4200 m and >3200 m thick, have been recognized in the Mesohellenic piggy-back basin of middle Eocene to middle Miocene age, where submarine fans have accumulated unconformably over an ophiolite complex. The hydrocarbon potential is indicated by the presence of kerogen types II/III with minor amounts of type I; the evidence is mostly for wet gas and gas, with minor oil. Source rocks are the middle Eocene to lower Oligocene Krania and Eptachori formations, of up to 2000 m total thickness, reaching maturation during the early Miocene. The source rocks consist of outer fan and basin plain deposits. They are conformably overlain by the lower member (late Oligocene) of the up to 2600 m thick Pentalophos Formation, which consists mostly of thick submarine sandstone lobes. Possible stratigraphically trapped reservoirs include the lower member of the Pentalophos Formation, which overlies source rocks, as well as limestones tectonically intercalated within the ophiolite complex, underlying the source rocks. Traps may have formed also on the western side of an internal thrust (Theotokos Thrust), which influenced the evolution of the depocentres.     

A study of natural and artificially generated light hydrocarbons (C4–C13) in source rocks and petroleum fluids from offshore Mid-Norway and the southernmost Norwegian and Danish sectors

The “free” or “natural” light hydrocarbon composition obtained by thermal extraction-GC of source rock samples is compared with the light fraction generated by pyrolysis products of the kerogens. Even though there are large differences between the composition of the “free” C₄–C₁₃ hydrocarbon fraction and the same fraction generated by pyrolysis, some characteristics have been detected which can be used interchangeably for both data types. Visual inspection of gas chromatograms from thermal extracts and pyrolysates indicates that in particular the relative content of m+p xylene corresponds well between these two analytical methods. The source rock samples used are Upper Jurassic marine shales and Middle and Lower Jurassic coals and coaly shales from offshore Mid-Norway and Denmark. More detailed analysis of the data shows that the most effective parameter which can distinguish between different source rock types in both thermal extracts and pyrolysates is the m+p xylene/nC₈ ratio. This parameter has been used to derive classification diagrams for interpreting the source of light hydrocarbons of both natural petroleum fluids analysed by gas chromatography and the same fraction generated by pyrolysis of asphaltenes from the fluids.The model was first tested on 17 natural petroleum fluids from Mid-Norway since a comprehensive study of light hydrocarbon distributions already has been published. Further, the parameter was applied to correlate with asphaltene pyrolysates of the fluids from Mid-Norway and a total of 22 natural oils and condensates from the southernmost Norwegian and Danish sectors.     

碳酸盐岩干酪根催化降解生烃过程及动力学研究

以甘肃平凉地区奥陶系碳酸盐岩干酪根为对象,利用热模拟实验方法和化工催化原理,从热解生烃组成特征、生烃量及生烃动力学等方面考察了不同介质对干酪根热解生烃过程的影响。结果表明,碳酸盐岩对干酪根生烃过程具有反催化作用,随着温度的增加,反催化作用越明显。膏岩CaSO₄则表现出正催化作用,各种盐类对干酪根生烃过程影响较小。干酪根热解动力学研究表明,生烃动力学参数活化能E与视频率因子A之间不是独立变化的,它们之间存在一定的关系,即:E与lnA呈线形关系,这对于认识碳酸盐岩干酪根的化学结构及热解生烃机理具有一定的参考价值。     

Stability and hydrogenation of polycyclic aromatic hydrocarbons during hydropyrolysis (HyPy) – Relevance for high maturity organic matter

A series of hydropyrolysis (HyPy) experiments have been conducted on a small suite of authentic polycyclic aromatic hydrocarbons (PAHs: coronene, pyrene and perylene) to investigate the HyPy behaviour of these PAHs. This information may help in the interpretation of the structural significance of aromatic HyPy products, often detected in high abundance, from high maturity kerogens. The PAHs were separately treated by HyPy and were all susceptible to some extent of hydrogenation. Perylene also decomposed into low molecular weight aromatics (e.g. methylbiphenyls). Structurally, perylene is much less stable than the more condensed PAHs coronene and pyrene. The total product concentrations (wt% of starting PAH) from all HyPy experiments were consistently less than 100 wt%, probably due to either the condensation of semi-volatile products on walls of the transfer line prior to reaching the HyPy trap or the inefficient cold trapping of highly volatile products. Hydrogenation of PAHs was prevalent and was found to be significantly influenced by the addition of a Mo-S based catalyst and potentially the C/Mo ratio, but largely independent of the two final temperatures used (520 °C and 550 °C). The fully aromatised and hydrogenated products for any stable ring system may provide a general indication of the size distribution of aromatic units within the kerogen structure.