固体13C核磁共振技术在石油地球化学研究中的应用

生烃母质的结构及其演化特征是石油地球化学研究的重要课题之一,随着新的分析测试方法的出现,生烃母质结构组成的研究已从基本的元素分析向官能团分析方向发展。固体核磁共振¹³C（NMR）分析已成为研究物质结构及其演化的一种有效手段,它可以测定不同类型含碳官能团的定量分布,从而计算各种结构参数,提供有关碳骨架最直接的重要信息。将这些结构信息从烃源岩的生烃潜力评价、烃源岩的生烃演化过程及机理、烃源岩的热演化判定等角度考虑实际存在的地质问题,发现脂族碳是油气的主要贡献者,油气潜力碳含量的高低决定了烃源岩生烃潜力的大小,芳核平均结构尺寸是有效的热演化衡量标尺。固体¹³C核磁共振分析为石油地球化学的研究打开了新局面。     

Effects of natural organic matter from sediments on the growth of marine gas hydrates

Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.     

天然烧变高岭石中水铝英石的发现

作者用DTA、TG、XRD、29Si和27AlMASNMR等手段对我国北方的一些天然烧变高岭石及其热处理产物进行了研究．首次在天然烧变高岭石的29Si魔角旋转核磁共振谱中（MASNMR）记录到了-79．0×10－6位置附近的水铝英石的特征29Si信号，说明在一定的自然条件下，经过水的化学作用，变高岭石可以转变成水铝英石。但是，水铝英石是一种非晶质相物质，它不稳定，易脱失结构水而转变成其它物相，这些发现对完善高岭石的相变理论具有重要的科学意义     

Early chlorin diagenesis in a recent aquatic sediment

Chlorophylls a and b, pheophytins a and b, pheophorbides a and b and pyropheophorbide a were identified in a Recent sediment (Priest Pot from Cumbria, U.K.) by laboratory preparation and structure elucidation by NMR and FAB-MS, and HPLC coelution with sedimentary extracts. Quantitative depth profiles revealed a steady decrease of the ratios of chlorophylls to pheophytins, and also a different but fairly constant a to b ratio for the pheophytins and the chlorins.     

Developments in high-resolution solid-state13C NMR spectroscopy of coals

The recent development of “second generation” NMR experiments on coals is discussed in this paper. Such experiments have three aims: (1) To determine the extent to which quantitative aromaticity measurements can be made on coals by cross polarization-magic angle spinning (CP/MAS); (2) To obtain more detailed information on coal structure and reactivity than that given by the simple aromaticity measurements possible at the time; (3) To follow reaction pathways when coal is chemically modified. In this plenary lecture the relevant literature is reviewed, and new experimental work in all three areas outlined above is reported. Experimental evidence is presented which shows that aromaticity measurements on a bituminous coal by cross polarization (CP) or single pulse techniques give identical results. Relaxation data for naphthalene polymers suggest that these structures in coal are seen in CP experiments. Dipolar dephasing experiments suggest that the average size of the coal vitrinite molecule does not increase with increase in coal rank due to aromatic substitution reactions. Various relaxation experiments demonstrate how different carbon types can be distinguished in both¹³C-labelled and unlabelled coals.     

The nature of olefins and carboxyl groups in an Australian brown coal resin

The chemical structure of the resin from an Australian soft brown coal (Yallourn) has been investigated by cross-polarization nuclear magnetic resonance spectroscopy with magic angle spinning (¹³C CP MAS NMR). Some additional solution ¹H and ¹³C data were also obtained. Solid-state experiments were performed with and without a delay period before data acquisition. The resulting free induction decays were Fourier transformed with respect to acquisition time and delay period to produce two-dimensional solid-state spectra. Assignments made from the spectra clearly demonstrate that the gross chemical structure of the Yallourn resin is best described as a polymerized diterpenoid with one axial carboxylic group and two double bonds. One double bond is trisubstituted, the other is monosubstituted. After consideration of various mechanisms for polymerization of diterpenoid units during biogenesis and coalification, it was concluded that polymerization occurs at the C₁₅ carbon atoms in the diterpenoids without cyclization of the methylene units at C₈.     

Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state C nuclear magnetic resonance

Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studies by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing ¹³C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage.     

Analyses of insoluble residues of altered organic matter by C CP/MAS nuclear magnetic resonance

Alteration phenomena affecting organic matter during diagenesis frequently lead to the formation of residues almost insoluble. Data from ¹³C CP/MAS nuclear magnetic resonance analyses (NMR) of these residues have been compared to those obtained by other techniques such as elemental analysis, infrared spectroscopy, Rock-Eval pyrolysis or gas chromatography. Three examples of alteration phenomena have been chosen: the artificial and natural oxidation of coals, the biodegradation of oils and solid bitumens, and the radiolytic degradation of organic matter. NMR results and those obtained by other techniques converge on similar general conclusions. Additional information can be extracted from ¹³C NMR data: e.g. definition of the phenol/carbonyl ratio, transformation of the aromatic network and aromatic ring substitution. These comparisons are good evidence for the reliability of non-destructive analysis of the insoluble fraction of altered organic material by ¹³C CP/MAS NMR.     

Occurrence and significance of pyrochlorins in a lake sediment

The occurrence of pyrochlorophyll a and pyrophaeophytins a and b in the bottom sediments of a small eutrophic lake (Priest Pot, Cumbria, U.K.) is reported on the basis of HPLC coinjection with standards. Assignment of pyrophaeophytins a and b was confirmed by FAB mass spectrometric and nuclear magnetic resonance studies of the isolated components and comparison with standards. The co-occurrence of pyrochlorins with their non-pyro counterparts, even in a surface sediment, shows that decarbomethoxylation can occur at the very earliest stages of the Treibs diagenetic pathway linking the chlorophylls and sedimentary porphyrins.     

基于形态小波的核磁共振测井信号去噪及现场应用研究

核磁共振测井中采集到的回波串信号十分微弱,而背景噪声很强,使信噪分离困难。为解决这一问题,引入了结合数学形态学的特征识别和小波分解的多分辨率分析特性的形态小波方法。讨论了方法的数据基础和应用步骤,并与小波软阈值方法处理结果进行了对比分析。实测数据处理结果表明:形态小波去噪方法具有良好的细节保留和抗噪声能力,去噪效果优于小波软阈值滤波方法;在消除测井信号随机噪声的同时,能很好地保留信号的波形和特征,在较低信噪比下仍可有效地提取测井信号的有用信息,提高了T2谱的反演精度。