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1.
High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm−1 at ambient temperature for hydrous Mg-ringwoodite (γ-Mg2SiO4) up to 30 GPa. The main feature in the OH stretching region is an extremely broad band centred at 3,150 cm−1. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm−1 and an absorption plateau persist with a maximum wavenumber of 3,800 cm−1. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.  相似文献   
2.
煤岩显微组分热解气相色谱特征与化学结构剖析   总被引:3,自引:0,他引:3       下载免费PDF全文
煤结构是目前地球化学研究领域中的一个难点,但却具有极其重要的理论及实际意义,本文采用分步热解气相色谱技术将树皮体,镜质体和丝质体分解为分子量较小的可测定的有机化合物,在此基础上,据不同温度下热解产物的组成特征来还原显微组分的化学结构,实验结果表明,煤显微组分主要由四大类官能团组成,一是热稳定性较低的NOS杂原子官能团;二是脂族(脂链、脂环)结构;三是苯、烷基苯(甲苯、二甲苯)、萘等芳香族化合物,四是热稳定性很高的难以分解的稠环芳烃。上述四类化合物集中于显微组分的不同结构简单中,树皮体和镜质体结构单元外侧主要由热稳定性较低的杂原子化合物以及分子量较小的苯和烷基苯组成,而丝质体结构单元外侧则主要以短链脂族结构为主,三组分结构核部由热稳定性很高的难以分解的稠环芳烃组成。连结核部稠环芳烃与结构单元外侧杂原子等官能团的主要是热稳定性较高的脂链结构,煤显微组分热成烃主要按结构中各官能团键的强弱随热演化程度的加深依次脱除,生成油气,基本上属平行独立依次反应机制,亦“官能团脱除型”,此外,还包括少量的长链脂族结构裂解为短链脂肪烃的“解聚”过程。  相似文献   
3.
A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.  相似文献   
4.
It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.  相似文献   
5.
Fluid-undersaturated experiments were conducted to determine the phase relations in the simplified peridotite system MgO-SiO2-H2O (MSH) at 11.0-14.5 GPa and 800-1400 °C. Stability relations of dense hydrous magnesium silicates (DHMSs) under fluid-undersaturated conditions were experimentally examined. From the fluid-absent experimental results, we retrieved thermodynamic data for clinohumite, phase A, phase E, and hydrous wadsleyite, consistent with the published data set for dry mantle minerals. With this new data set, we have calculated phase equilibria in the MSH system including dehydration reactions. The dehydration reactions calculated with lower water activities of 0.68-0.60 match the fluid-present experiments of this study above 11.0 GPa and 1000 °C, indicating that considerable amounts of silicate component were dissolved into the fluid phase. The calculated phase equilibria illustrate the stability of the post-antigorite phase A-bearing assemblages. In the cold subducting slab peridotite, phase A + enstatite assemblage survives into the transition zone, whereas phase A + forsterite + enstatite assemblage forms hydrous wadsleyite at a much shallower depth of about 360-km. The slab is subducted with no dehydration reactions occurring when entering the transition zone. The phase equilibria also show the high temperature stability of phase E. Phase E is stable up to 1200 °C at 13.5 GPa, a plausible condition in the mantle of relatively low temperature, i.e., beneath subduction zones. Phase E is a possible water reservoir in the mantle as well as wadsleyite and ringwoodite.  相似文献   
6.
从吐哈盆地侏罗纪煤中分离富集了藻类体、孢子体、角质体、镜质体、基质镜质体和丝质体6种主要显微组分,进行了热解及热模拟实验,并对各显微组分热模拟生成的产物热解油进行了碳同位素组成等分析。各显微组分热解生烃潜力及其热解产物热解油的碳同位素组成表明,煤系有机质中藻类体的生油潜力最高,生成的液态烃类的碳同位素组成最轻;孢子体、角质体等陆源富氢组分生烃潜力低于藻类体,生成的液态烃类的碳同位素组成重于藻类体生成的液态烃类,与煤系含油气盆地中原油的碳同位素组成基本一致。这些富氢显微组分应该是煤系有机质中主要的生油显微组分。镜质体和基质镜质体的生油潜力相对较低,其生成的液态烃类的碳同位素组成比一般煤系原油重得多,而且这些组分本身对液态烃具有较强的吸附力,尽管其在煤系有机质中所占的比例很大,仍然难以成为生成液态石油的主要显微组分,只能在高成熟演化阶段成为良好的生气显微组分。丝质体等惰性组分生烃潜力极低,不可能成为生油组分。此外,结合原煤的显微组分组成、生烃潜力和元素分析,提出仅仅以壳质组的含量高低来评价煤的生烃潜力不完全可靠,热解是经济、快速、有效的评价方法。  相似文献   
7.
Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C1, C2–C5, C6–C15 and C15+). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.  相似文献   
8.
Stem wood of the Angiosperm Calluna vulgaris (Scotch heather), isolated at different depths from a selection of raised bog peat deposits, was chemically characterized using in-source pyrolysis mass spectrometry (Py-MS) and Curie-point pyrolysis gas chromatography mass spectrometry (Py-GC-MS). Light microscopy was performed to relate mass spectrometric characteristics with anatomical features. Peatified wood samples, isolated from increasing depth show a gradual decrease in carbohydrate content. This decrease in anatomically reflected in a selective removal of secondary cell wall material from the fibre-tracheids and wood parenchyma. During prolonged peatification a selective removal of hemicellulose sugars is observed, while a part of the cellulose fraction is preserved. This highly resistant cellulose is mainly located in the secondary cell walls of the vessels. The lignin macromolecule is preserved, but a gradual decrease in syringyl to guaiacyl ratio (S/G) is observed during peatification. Because no increase in catechol and phenolic compounds is observed, we conclude that S/G shifts are due to removal the of syringyl-rich secondary cell wall material and the retention of guaiacyl-rich compound middle lamella. Small chemical changes in the lignin macromolecule involve shifts in oxygen substitutions on the aliphatic side chains of the methoxyphenolics and the occurrence of aromatic acids.  相似文献   
9.
The natural thermal evolution of type III coals (Humic origin) is expressed during diagenesis by a loss of oxygen as CO2 and H2O. Other phenomena such as oxidation can cause extensive geochemical modifications and may complicate the effects of simple maturation.Humic coals from the Jurassic in southeastern Utah were studied by elemental analysis, Rock-Eval pyrolysis and infrared spectroscopy. In a van Krevelen diagram (atomic H/C vs atomic O/C), the samples fall within the envelope defined by 860 reference humic coals covering the entire range of diagenesis. Nevertheless, various criteria (geochemical, petrographic, geological and microscopic) cast doubt upon the interpretation that such a distribution of coal composition results from thermal maturation.The same criteria indicate the intervention of redox phenomena. Comparison of our results with those from artificial and natural oxidation shows that these coals were subjected to an oxidation process different from ordinary late alteration. This process was probably due to circulation of highly oxidizing saline water causing oxygen fixation and the transformation of carboxyls into carboxylate anions. The cations that were fixed are oxygenated and certainly contain calcium, but also uranium and perhaps several other cations (V, Mo, Fe...). Emphasis is placed on possible mechanisms that cause such phenomena.  相似文献   
10.
Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C31. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.  相似文献   
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