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1.
The Py-GC/MS results of the study carried out on two groups of vitrinites (perhydrous and non-perhydrous) of different age and properties and on a trimaceralic coal associated with one of the perhydrous group are discussed. Such a study provides information about the effect of natural hydrogen enrichment on vitrinite structure at the molecular level. Moreover, the influence of the different conditions in the sedimentary environment on the chemical structure of the vitrinite is also discussed. This influence is inferred through differences in the distribution and relative amount of phenolic compounds found in the pyrolysates from two samples of two different coal-beds in the same basin but formed under different paleoenvironmental conditions. For vitrinites with a high H/C atomic ratio, despite having a strong perhydrous character, their pyrolysates exhibit the highly phenolic signature typical of lignin-derived material with only minor aliphatic compounds. Thus, the major chemical structural elements in these vitrinites are simple phenols with a high contribution of para alkyl-substituted derivatives. However, there is no parallel relationship between the evolution of the oxygenated functionalities and the reflectance values. From the results obtained a coalification pathway where hydrogenation processes predominate over thermal ones is proposed. The presence of resin-like substances and/or oils (which are two of the causes of natural hydrogen enrichment) in the molecular structure of vitrinites have, therefore, affected the normal evolution of the lignin and contributed to the special properties of this type of materials.  相似文献   

2.
The ratio of the abundance of the C19:1 isoprenoids 1-pristene and 2-pristene to the abundance of (nC17:1 + nC17:0) is significantly lower in pyrolysates of kerogens from highly anoxic depositional environments than in pyrolysates of kerogen if similar types and levels of catagenesis from more oxic organic facies. 13C-NMR analysis shows that the occurrence of lower relative concentrations of isoprenoid precursors also correlates with the occurrence of low proportions of oxygen-bonded carbon and high proportion of aliphatic carbon in kerogens. The ratio of 1-pristene to (n-C17:1 + nC17:0) can be correlated laterally and statigraphically within a basin. There is no clearly discernible dependence of relative isoprenoid concentration of kerogen type for oil-generative kerogens, although immature lignites have high 1-pristene/(nC17:1 + nC17:0) ratios.The 1-pristene/(nC17:1 + nC17:0) ratios in kerogens pyrolysates from the same organic facies decrease logarithmically with increasing catagenesis and can be correlated directly with measured vitrinite reflectance values. Geologic and experimental data imply that 1-pristene precursors are lost from kerogen more rapidly than the precursors of the C18 isoprenoid.The lower relative isoprenoid concentrations observed in anoxically deposited kerogens appear to be the result of the enhanced preservation of normal alkyl groups and the enhanced formation of free isophrenoids early in the sequence of kerogen alteration. These results are significant to the use of isoprenoids as geochemical marker oils, bitumens, and kerogens and to the determination of the structure and diagenesis of isoprenoid precursors.  相似文献   

3.
镜质组是腐殖煤中最主要的显微组分,其结构极为复杂。采用单一的实验手段,很难对镜质组结构进行深入研究。采用低温热解、高温热解及TMAH在线甲基化热解3种瞬时热解方法,对镜质组结构中吸附烃、与大分子相连的支链基团中非极性及极性组分分别进行研究。实验结果表明,吸附烃特征决定于镜质组类型及成熟度两种因素。均质镜质体吸附烃以芳烃为主,而基质镜质体吸附烃以正构脂肪烃为主。热解产物中,芳烃所占比例随基质镜质体成熟度的增加而变大;基质镜质体高温热解主要产物为正构脂肪烃,其次为芳烃和酚类,而均质镜质体高温热解主要产物为酚类,其次为芳烃,脂肪烃所占比例较小。TMAH甲基化研究表明,镜质组结构中含有丰富的脂肪酸,而脂肪酸有可能是煤成油的主要母质来源之一。镜质组不同条件下的热解产物特征说明,不同镜质组具有明显的结构差异,并对其生烃特征具有重要影响。   相似文献   

4.
Immature vitrinite samples from a Miocene lignite seam of western Germany (H/C = 1.14, O/C = 0.41) and alginite concentrates from a Tasmanite deposit of Australia (H/C = 1.60, O/C = 0.10) were pyrolyzed in a stream of argon at heating rates of 0.1 and 2.0°C/min up to temperatures varying from 200 to 670°C. The solid maceral residues were subjected to elemental and microscopical analysis and studied by IR and 13C CP/MAS NMR spectroscopy with respect to structural modifications.The maximum pyrolytic weight loss amounts to 60% of the initial organic matter in the case of vitrinite and to 85% for alginite, the onset of degradation reactions being shifted to higher temperatures with increasing rate of heating. Both infrared and NMR spectra of the vitrinite samples indicate a rapid decomposition of the cellulose component upon heating whereas lignin related structures such as aromatic ether linkages remain remarkably stable. The main hydrocarbon release from vitrinite occurs at very early evolution stages (Tmax = 296°C, Rm = 0.20% at 0.1°C/min; Tmax = 337°C, Rm = 0.23 at 2.0°C/min). Hydrocarbon generation from alginite requires higher temperatures (Tmax = 388 and 438°C) and is completed within a distinctly narrower temperature range.The pronounced increase of vitrinite reflectance between 350 and 670°C seems to be associated with a rather time-consuming reorganization of the residual organic material. The concomitant growth of polyaromatic units is illustrated by the increasing intensity ratio of the aromatic ring stretching vibration bands at 1600 and 1500 cm−1. These reactions are moreover marked by increasing loss of phenolic oxygen and by increasing conversion of aliphatic carbon into fixed aromatic carbon.  相似文献   

5.
To study the detailed structural and isotopic heterogeneity of the insoluble organic matter (IOM) of the Murchison meteorite, we performed two types of pyrolytic experiments: gradual pyrolysis and stepwise pyrolysis. The pyrolysates from the IOM contained 5 specific organic groups: aliphatic hydrocarbons, aromatic hydrocarbons, sulfur-bearing compounds, nitrogen-bearing compounds, and oxygen-bearing compounds. The release temperatures and the compositions of these pyrolysates demonstrated that the IOM is composed of a thermally unstable part and a thermally stable part. The thermally unstable part mainly served as the linkage and substituent portion that bound the thermally stable part, which was dispersed throughout the IOM. The linkage and substituent portion consisted of aliphatic hydrocarbons from C4 to C8, aromatic hydrocarbons with up to 6 rings, sulfo and thiol groups (the main reservoirs of sulfur in the IOM), and carboxyl and hydroxyl groups (the main reservoirs of oxygen). However, the thermally stable part was composed of polycyclic aromatic hydrocarbons (PAHs) containing nitrogen heterocycles in the IOM. Isotopic data showed that the aliphatic and aromatic hydrocarbons in the linkage and substituent portion were rich in D and 13C, while the thermally stable part was deficient in D and 13C. The structural and isotopic features suggested that the IOM was formed by mixing sulfur- and oxygen-bearing compounds rich in D and 13C (e.g., polar compounds in the interstellar medium (ISM)) and nitrogen-bearing PAHs deficient in D and 13C (e.g., polymerized compounds in the ISM).  相似文献   

6.
华北太原组镜质组中的超微类脂体及其煤性质异常原因   总被引：1，自引：0，他引：1  
王飞宇  傅家谟 《沉积学报》1995,13(3):107-116
利用超薄切片透射电镜分析技术，对华北太原组和山西组煤中镜质组的超微结构和组分进行了分析，确认太原组镜质组中含有较丰富的超微类脂体，且超微类脂体主要来自菌藻类，山西组和太原组镜质组中超微类脂体数量存在明显差异。证实镜质体中超微类脂体数量和其化学性质紧密相关。从超微组分层次解释了山西组和太原组镜质组性质差异的原因，并分析讨论了太原组煤性质异常性的原因和煤还原程度问题，提出成煤过程中明显菌藻类低等生物贡献是太原组煤性质异常的一个重要原因。  相似文献   

7.
Solid state 13C NMR techniques of cross polarization with magic-angle spinning, and interrupted decoupling have been employed to examine the nature of the organic matter in eight kerogen concentrates representing five Tertiary deposits in Queensland, Australia. The NMR results show that five of the kerogens have high proportions of aliphatic carbon in their organic matter and correspond to Type I–II algal kerogens. Three of the kerogens, derived from carbonaceous shales, have a high proportion of aromatic carbon in their organic matter and correspond to Type III kerogens. The fractions of aliphatic carbon in all the kerogens, regardless of type, are shown to correlate with the conversion characteristics of the corresponding raw shales during Fischer assay. Interrupted decoupling NMR results show the presence of more oxygen-substituted carbon in the carbonaceous shales, which may account for the greater CO2 evolution and phenolic materials found in the pyrolysis products of the carbonaceous shales.  相似文献   

8.
Coal as a source rock for oil: a review   总被引：2，自引：0，他引：2  
The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and 13C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO2 and CH4 could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.  相似文献   

9.
《International Geology Review》2012,54(15):1852-1872
Medium-grade metabasites and metapelites from the Cajamarca Complex (Central Cordillera of Colombia) are in fault contact with the Jurassic Ibague batholith and show a penetrative foliation, locally mylonitic, suggesting intense dynamic–thermal metamorphism. The amphibolites are composed of calcic amphibole + epidote + plagioclase + quartz plus rutile + titanite + apatite + carbonate as accessory phases. Chlorite and albite appear as retrograde replacements. The metapelites are mainly composed of phengite + quartz + garnet + chlorite, plus epidote + albite + apatite + titanite + haematite as accessory phases. Bulk geochemistry of the amphibolites indicates basaltic protoliths with a mid-ocean ridge basalt (MORB) signature, although enrichment in the mobile large-ion lithophile elements compared to MORB suggests pre- and/or syn-metamorphic alteration by fluids. Peak pressure–temperature determinations for both types of rocks are similar, ranging 550–580°C and 8 kbar (approximately 26 km depth and an apparent geothermal gradient of 22°C/km). 40Ar-39Ar dating of amphibole from two amphibolite samples and one phengitic mica from a pelitic schist yielded plateau ages of 146.5 ± 1.1 Ma and 157.8 ± 0.6 Ma, and 157.5 ± 0.4 Ma, respectively. These Late Jurassic ages contrast with previously published (Permian)Triassic ages of metamorphism in the Cajamarca Complex. Taken together, our data indicate tectonic-driven burial of oceanic supracrustal sequences down to mid-crustal depths during Late Jurassic times and are best explained as the result of terrane collision-related metamorphism and deformation in a fore-arc/volcanic-arc environment of the active western margin of Gondwana rather than as a result of Jurassic thermal–metamorphic resetting of a (Permian)Triassic metamorphic sequence during intrusion of the Jurassic Ibague batholith. Our results represent the first report of Jurassic terrane collision tectonics involving supracrustal oceanic rocks in the northwestern margin of Gondwana in Colombia.  相似文献   

10.
Examination of a series of coalified gymnospermous woods ranging in rank from brown coal to subbituminous coal by solid-state 13C NMR and analytical pyrolysis has provided sufficient information to construct structural models depicting the changes that occur to lignin, the primary precursor of vitrinite, during coalification. Progressive changes in the chemistry of coalified wood suggest the following series of reactions: (1) demethylation to form catechol-like structures that are dominant components of brown coal and lignite A; (2) cleavage of aryl ether linkages to form phenols and reactive carbocations that alkylate the catechol rings; (3) dehydration of the catechol rings; (3) dehydration of the catechol-like structures to form the structures of subbituminous coal dominated by alkylphenols; and (4) reduction of the 3-carbon alkyl side chain derived from lignin to form propyl substituents. The models developed for each stage of coalification are derived from chemical modifications of the structure of lignin.  相似文献   

11.
This paper presents geological settings, stratigraphy, coal quality, petrography, reserves and the tectonic history of the Mongolian coal-bearing basins. This is based on a synthesis of the data from nearly 50 coal deposits. The results of ultimate and proximate analyses, and calorific value, maceral composition and vitrinite reflectance data is given.The coal deposits of Mongolia tend to become younger from west to east and can be subdivided into two provinces, twelve basins, and three areas. Main controlling factor of coal rank is the age of the coal bearing sequences. Western Mongolian coal-bearing province contains mostly high rank bituminous coal in strata from Late Carboniferous. The basins in southern Mongolia and the western part of central Mongolia have low rank bituminous coal in strata from the Permian. The northern and central Mongolian basins contain mainly Jurassic subbituminous coal, whereas the Eastern Mongolian province has Lower Cretaceous lignite. The Carboniferous, Permian and Jurassic coal-bearing sequences were mainly deposited in foreland basins by compressional tectonic event, whereas Cretaceous coal measures were deposited in rift valleys caused by extensional tectonic event. Petrographically, Mongolian coals are classified as humic type. Vitrinite/huminite groups of Carboniferous, Permian, and Cretaceous coal range from 44.9% to 82.9%. Inertinite group varies between 15.0% and 53.3%, but liptinite group does not exceed more than 7%. Jurassic coals are characterized by high percentages of vitrinite (87.3% to 96.6%) and liptinite groups (up to 11.7%). This might be explained by paleoclimatic conditions. Mongolian coal reserves have been estimated to be 10.2 billion tons, of which a predominant portion is lignite in the Eastern Mongolian province and coking coal in the South Gobi basin.  相似文献   

12.
The cuticles and cuticle-free compressions of three Carboniferous medullosan seed-fern leaf species (Macroneuropteris scheuchzeri, Neuropteris ovata var. simonii and Alethopteris lesquereuxii) were analyzed by elemental, 13C nuclear magnetic resonance (NMR), micro-FTIR (Fourier transform infrared) and coal petrographic techniques. The 13C NMR spectra of the cuticle-free compressions and the associated whole coal (high volatile A/B bituminous coal rank) are generally similar and consist of a large aromatic carbon peak, a smaller aliphatic carbon peak and a shoulder on the aromatic peak, representing phenolic carbons. In contrast, the 13C NMR spectra of the cuticles from the same leaves have a predominant peak for aliphatic carbons and a much smaller aromatic carbon peak. This difference in aromaticity between the cuticles and the cuticle-free compressions is also reflected in the higher atomic H/C ratios of the cuticles. Micro-FTIR spectra of the cuticles show oxygenated functional groups (carboxyl and ketone) similar to those in modern cuticles but their most characteristic feature is very strong bands in the aliphatic stretching region. The cuticle-free compressions (mainly vitrinite), in turn, show the absence or significant reduction in oxygenated functional groups, reduction in aliphatic stretching bands and, usually, increased absorbance of aromatic out-of-plane deformation in the 700–900 cm−1 region. Fluorescence spectra for the cuticles from all three species show a great similarity with a λmax at 580–590 nm, probably reflecting a similardegree of coalification, which is consistent with the similar vitrinite reflectance (Rr) and H/C and O/C ratios of the cuticlefree compressions.These results indicate that leaf cuticle-free compressions, which were initially cellulose rich ( 90% cellulose and hemicellulose, < 10% lignin), can alter, during peatification and coalification, to a macromolecular structure similar to that of coalified wood (initially 50% cellulose and hemicellulose, 30%–50% lignin). Thus, a lignin-enriched structure is not a prerequisite for the formation of the macromolecular structure of vitrinite. In addition, the micro-FTIR spectra reveal the complexity of the molecular structure in coalified seed-fern leaves. The micro-FFIR data reveal some significant differences among the cuticles that may be of chemotaxonomic value. Clearly, a combination of macro- and micro-techniques offers a better basis for the interpretation of the molecular structure of pre-macerals and their alteration during peatification and coalification. Also, the data presented in this paper provide important new information that extends the data from morphological and cuticular taxonomic studies of some seed ferns. The data are encouraging preliminary advances in the chemotaxonomy of medullosan seed fern species.Pyrolysis-gas chromatography (PY-GC) data for the cuticles of three seed-fern leaves indicate distinct chemical signatures for the two neuropterid leaves as compared to the Alethopteris leaf. This perhaps indicates a chemotaxomic factor, or it could be related to the greater thickness of the cuticle of Alethopteris. Mass spectrometric data are needed to identify individual components in the PY-GC chromatograms.  相似文献   

13.
The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (13C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. 13C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CHxO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (fa), O/C and relative proportions of various carbon types estimated by 13C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.  相似文献   

14.
《Chemical Geology》2006,225(1-2):77-90
Using density-gradient centrifugation, within-sample heterogeneity in C/N, δ13C, and δ15N was determined for a sample of the Blue Gem coal bed (Middle Pennsylvanian, Duckmantian (Westphalian B), Breathitt Formation) and related to maceral (petrographically identifiable organic component) composition. Relatively pure macerals were separated by density, with purities up to 99% in the case of vitrinite in fractions around 1.3 g/mL. Lower density fractions (∼ 1.2 g/mL) contain predominantly liptinite (∼ 75%) but also significant amounts of vitrinite (∼ 20%). Denser fractions contain increasing amounts of inertinite, with several fractions between 1.37 and 1.44 g/mL containing > 98% total inertinite. Within these denser fractions, semifusinite concentrated at lower densities than did fusinite. The separation of macerals by density allowed a more detailed evaluation of the isotopic composition of relatively pure macerals within a single coal. δ13C becomes increasingly heavy across the density gradient, with δ13C values being lightest in the liptinites, followed by vitrinite, and then semifusinite and fusinite; by contrast, δ15N becomes lighter across the same density range. C/H increases with density, reflecting a general decrease in aliphatic components and increase in aromatic components. C/N follows a similar pattern, ranging from < 40 to over 100, increasing significantly at densities > 1.32, the point at which inertinite macerals begin to predominate over vitrinite.The isotopic composition of macerals reflects chemical composition, which in turn reflects: 1) the original composition of plant tissues from which the macerals originated; 2) early diagenetic changes; and 3) changes during coalification. Macerals derived from lipid-rich precursor materials (liptinites) have more depleted δ13C values (∼ 2‰) relative to those derived from woody tissues (vitrinite). Fusinized material, derived from fossil charcoal, has δ13C values enriched by ∼ 0.5‰ compared with the vitrinite, consistent with the results from combustion experiments using modern plant tissues. Vitrinite fractions have enriched δ15N values relative to inertinite fractions, which may reflect early diagenetic changes in woody tissues involving preferential loss of 14N, possibly due to bacterial activity during the peat-forming stage. Due to the within-sample variability in carbon isotopic composition reported here, it is suggested that chemostratigraphic studies based on Type III kerogen (including both dispersed organic matter and coals) carefully consider the associated effects of variability in maceral composition.  相似文献   

15.
Soil organic matter (SOM) is one of the earth’s largest reservoirs of actively cycled carbon and plays a critical role in various ecosystem functions. In this study, mineral soils with the same parent material and of similar approximate age were sampled from the same climatic region in Halsey, Nebraska to determine the relationship between overlying vegetation inputs to SOM composition using complementary molecular level methods (biomarker analyses and solid state 13C nuclear magnetic resonance (NMR) spectroscopy). Soil samples were collected from a native prairie and cedar and pine sites planted on the native prairie. Free and bound lipids isolated from the pine soil were more enriched in aliphatic and cutin-derived compounds than the other two soils. Cinnamyl type lignin-derived phenols were more abundant in the grassland soil than in the pine and cedar soils. Acid to aldehyde ratios (Ad/Al) for vanillyl and syringyl type phenols were higher for the pine soil indicating a more advanced stage of lignin oxidation (also observed by 13C NMR) in the soil that has also been reported to have accelerated carbon loss. In agreement with the more abundant aliphatic lipids and cutin-derived compounds, solid state 13C NMR results also indicated that the SOM of the pine soil may have received more aliphatic carbon inputs or may have lost other components during enhanced decomposition. The observed relationship between vegetation and SOM composition may have important implications for global carbon cycling as some structures (e.g. aliphatics) are hypothesized to be more recalcitrant compared to others and their accumulation in soils may enhance below ground carbon storage.  相似文献   

16.
Combining vitrinite reflectance (VR) and fluorescence alteration of multiple macerals (FAMM) analyses provide insights into the chemical nature of vitrinites (i.e., perhydrous vs. orthohydrous vs. subhydrous compositions) in Permian Gondwana coals of the Paraná Basin, Brazil. The FAMM-derived equivalent VR (EqVR) values and relationships with VR can be determined according to calibration curves based largely on Permian Gondwana coals of eastern Australia.The analytical results indicate that vitrinites in the Paraná Basin coals studied generally range from orthohydrous to perhydrous, with interpreted VR suppression ranging up to 0.2% absolute for the most perhydrous case. The EqVR values of the Santa Catarina coals, which range from about 0.85% to 0.95% differ from VR values by about 0.10–0.15% absolute, potentially having significant implications on coal utilization.The causes of vitrinite reflectance suppression in the Paraná Basin coals are as yet poorly understood, but are likely to be related to a combination of factors.  相似文献   

17.
A fossil geothermal area is hosted by the Carboniferous, Permian and Bunter sandstones of the Offenburg intramontane trough in the central Black Forest. The hydrothermal alteration is identified on the basis of newly formed sericites, which appear as pseudomorphs after feldspar and filling of pore spaces. According to K–Ar dating of sericite, serititization occurred about 145 Ma ago (Jurassic). On the basis of 18O analyses of sericite, sericite composition and vitrinite reflectance, the hydrothermal fluids had temperatures of 150–210 °C. Because their electrolyte content was low, these fluids are assumed to have derived from meteoric water. A second pulse of electrolyte-rich hydrothermal fluids resulted in quartz overgrowths. Fluid mobilization seems to be linked to the disintegration of Pangaea and to reactivated fault systems extending from the crystalline basement into the intramontane sediments.  相似文献   

18.
An attempt has been made to study the petro-chemical characteristics of some high sulphur sub-bituminous coal samples from Makum coalfield, Assam, India. The proximate and ultimate analyes were carried out and forms of sulphur were determined and their relationships with the Maceral constituents (vitrinite, liptinite, and inertinite) were investigated. The macerals (vitrinite+liptinite+inertinite) have significant relationships (R2>0.500) with volatile matter and carbon, whereas weak correlations were seen with rest of the physico-chemical characteristics of the coals. The study reveals that these coals are rich in vitrinites and sulphur and are aromatic in nature. These coals have good hydrocarbon potential.  相似文献   

19.
Abstract

Small- and medium-sized basins are widely distributed, and some contain commercial gas reservoirs demonstrating their gas-generation potential. The Xuanhua Basin, which is a small-sized coal-bearing basin in north China, includes a promising target for shale-gas exploration in the Xiahuayuan Formation. In this study, we used this basin as a case study to assess the critical geochemical features for small or medium-sized basins to form commercial gas reservoirs. Total organic carbon (TOC) analysis, Rock-Eval pyrolysis, microscopic observation of macerals, vitrinite reflectance measurement and kerogen stable carbon isotope analysis were performed to characterise the organic geochemistry of the Xiahuayuan shales. The original total organic carbon (TOCo) content and hydrocarbon-generative potential (S2o) were reconstructed to further evaluate the gas-generation potential of these shales. In addition, geochemical data of shales from other similar-sized basins with gas discoveries were compared. The results showed that the kerogen from the Xiahuayuan Formation is Type III (gas-prone), and macerals are dominated by vitrinite. TOC values showed a strong heterogeneity in the vertical profiles, with most higher than 1.5?wt%. The measured Ro values ranged from 1.4 to 2.0%. However, thermal maturity was not correlated with the present-day burial depth with higher maturity in the wells closest to the diabase intrusion centre. The remaining generation potential (S2) averaged 0.91?mg HC/g rock, equal to 1.4?cm3 CH4/g rock, and the average amount of hydrocarbon generated was 4.33?cm3 CH4/g rock. In small and medium-sized basins, the TOC content of commercially developed gas shales ranged from 0.5 to 2.5?wt%, organic matter was mainly humic (gas-prone), and the burial depth was generally shallow. Biogenic gas reservoirs for commercial exploitation tend to have larger shale thicknesses (120–800?m) than thermogenic gas reservoirs (60–90?m).

  1. The Xiahuayuan Formation is a good gas-source rock with gas-prone kerogen type, relatively high TOC values and moderate thermal maturity.

  2. The average amount of hydrocarbon generated from the Xiahuayuan shales is about 4.33?cm3 CH4/g rock, indicating a potential to form a shale gas reservoir.

  3. Owing to the influence of diabase intrusions, the Xiahuayuan shales have entered the dry gas window at relatively shallow-buried depths.

  4. Small- and medium-sized basins have the potential to generate commercial gas reservoirs with the generated volume mainly a product of the thickness and maturity of black shales.

  相似文献   

20.
A variety of fungal melanins with natural 15N abundance are characterized by solid-state 13C and 15N NMR spectroscopy and are compared to solid-state 13C and 15N NMR spectra of organic matter from representative soils. In all solid-state 15N NMR spectra the peptide/amide region (−220 to −285 ppm) dominates with more than 70% of the total intensity. The region between −285 and −375 ppm, assigned to amino and ammonium groups, always contains more than half of the remaining intensity. The area in the region from −30 to −220 ppm, where aromatic heterocycles would show signals, makes up less than 10% of the total intensity. These findings call into question common structural models for melanins. The solid-state 13C NMR spectra, on the other hand, reveal large differences when the melanins are compared to each other, and to composts and soils. The concentration of the aromatic carbon varies from 5 to 40% in the melanin series. The ratio Caro/Ntot and Cali/Ntot were calculated, and confirm that nitrogen in these samples is bound in Ca-groups rather than in aromatic heterocyclic structures.  相似文献   

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