The application of FAMM (Fluorescence Alteration of Multiple Macerals) analyses for evaluating rank of Paraná Basin coals, Brazil

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.     

Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

Study of physical and chemical properties of vitrinites. Inferences on depositional and coalification controls

A detailed study of petrological, geochemical, textural and coking properties was carried out on vitrains from the Puertollano, Blanzy–Montçeau, Asturias and Teruel. The objective was to determine in depth the physical and chemical properties of a series of natural and pure vitrinites of different rank, and the influence that the sedimentary and post-sedimentary conditions had on them. It is demonstrated that although vitrains are almost entirely made up of the huminite/vitrinite maceral group they have a different composition, thermal behaviour and physical properties. Thus, geochemical and textural properties of Blanzy–Montçeau vitrains can be considered to be representative of the telinite, the major component in both samples (75% vol.) at the beginning of the bituminization stage (subbituminous/high volatile C bituminous coals). The characteristics of the Puertollano vitrains described here can also be attributed to the telocollinite (>80% vol.) for the high volatile C bituminous coal. Variations in physico-chemical properties between Puertollano and Blanzy–Montçeau vitrains are due to the differences in the initial composition of organic matter. Slight differences (i.e., bed moisture content or porosity) between vitrains from the two coal seams in the same basin can be attributed to their stratigraphic position. Several parameters such as S₂, HI, oil and extraction yield and fluorescent properties suggest that the Puertollano and Blanzy–Montçeau vitrains have a lower hydrocarbon potential. The relationships between geochemical and textural properties make it possible to distinguish between ‘normal' and perhydrous vitrains. The two different hydrogen-enrichment processes that occur in vitrains from the Teruel and Asturias basins can be distinguished from the extraction yield data.     

Quantitative chemical characterization of vitrinite concentrates using pyrolysis-gas chromatography. Rank variation of pyrolysis products

A series of hand-picked vitrinite samples from the Lower Kittanning Seam, Pennsylvania have been examined using quantitative pyrolysis-gas chromatography. These vitrinites ranged in rank from 0.59 to 1.71% reflectance, a rank range from high volatile C bituminous to low volatile bituminous. High molecular weight pyrolysis products included alkyl aromatic and phenolic compounds. Attempts have been made to correlate the pyrolysis product composition to rank parameters including vitrinite reflectance, volatile matter yield, carbon content, atomic H/C ratio and Rock-Eval determined T_max. Total yield of phenols was found to be strongly and inversely rank related. A clear relationship between C₈ alkyl-benzene yield and rank was not found for the sample set.     

华北太原组镜质组中的超微类脂体及其煤性质异常原因

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。     

Vitrinite recycling: diagnostic criteria and reflectance changes during weathering and reburial

The aim of this study was first to review or even identify reliable diagnostic criteria to distinguish recycled and autochthonous vitrinite particles and, second, to examine and try to explain the impact of weathering and reburial on optical changes (reflectance) of recycled material. The work was based on indigenous and recycled particles of two sample sets from two wells drilled in the Senegalese margin basin and the Ardèche paleomargin (SE France), respectively. In addition to reflectance measurements, the studied samples have also been analysed by Rock-Eval pyrolysis. For both sample sets, hydrogen index (HI) and oxygen index (OI) values suggest a type III organic matter of dominant terrestrial origin.Two main diagnostic criteria appear particularly useful to identify indigenous and recycled vitrinite particles: the first is the clear genetic relationship between telinite and collotelinite; the second is the presence of pyrite framboid inclusions in indigenous vitrinite. The pyrite–vitrinite association illustrates the relationship between sulphate reduction, pyritisation, and in situ organic matter transformation through gelification process. However, application of both diagnostic criteria requires some additional information about depositional conditions (i.e., anoxicity) and thermal maturity of the studied samples. Weathering has no or only very limited effect on vitrinite reflectance. During their new burial history, recycled vitrinites follow a reflectance evolution path close to that of inertinites and thus appear as transitional materials between vitrinite and inertinite macerals. Consistently, this behaviour implies that recycled vitrinite reflectance changes during burial diagenesis do not solely depend on their chemical composition but, most probably too, on combined chemical and structural changes inherited from their past burial history and from the impact of weathering during their recycling stage.     

西北侏罗纪低成熟煤中镜质组热解产物特征及地质意义

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。      

镜质体反射率热演化规律研究

镜质体反射率的演化并不是人们传统意义上认为的随着温度（深度）的增加成指数增加,而是分阶段演化的。通过对有机质热模拟实验数据和自然演化数据进行分析后发现镜质体反射率的演化可以分为明显的3段：1）缓慢变化阶段,随着温度的增加镜质体反射率缓慢地变化,2）中等快速阶段,随着温度的增加镜质体反射率相比较前一阶段增加速率有明显的加大,3）快速增加阶段,随着温度的增加镜质体反射率呈指数快速增加。这种分阶段的演化是由镜质体本身的化学组成和化学结构所决定的。镜质体反射率演化阶段的划分对于热历史的恢复以及认识镜质体的热演化机制和规律具有重要的意义。     

Possibilities of the utilization of micropetrographic parameters in the scientific classification of bituminous coals

Proposals for new scientific classifications of bituminous coals are based on micropetrographic parameters, i.e. vitrinite reflectance as a criterion of the coalification and maceral composition, presupposed to express the connection between the genetic peculiarities and physical, chemical, and technological properties of the coal mass. In the case of coals with high inertinite contents, however, the utilizability of these parameters meets with difficulties resulting from the subjectivity of determining the different transitional material and from insufficient knowledge of inertinite behaviour at higher temperatures. In the case of the maceral-variable bituminous coals produced in the Ostrava-Karviná Coal Basin, these insufficiencies are not important since it is especially the expression of the variability of the properties of isometamorphic vitrinites, which has decisive effects up-on the course of the thermo-chemical transformations, that is of principal importance to the scientific classification of these coals.In the first approximation, the properties of isometamorphic vitrinites may be expressed by the parameter (H/O)_at, closely connected with fluidity. While the micropetrographic parameters reflect in particular the peculiarities in the chemical structure of the aromatic parts of coal macromolecules, the parameter (H/O)_at expresses the properties of the non-aromatic structures of vitrinite, significantly affecting the course of its thermal degradation. The experimental results show that the value of the parameter (H/O)_at, fluidity and the course of degassing the coal of a lower coalification are independent of the maceral composition and vitrinite reflectance; also that the caking and coking properties of low-rank coals are especially dependent on the parameter (H/O)_at and partially on the micropetrographic parameters. All these facts should be taken into consideration in preparing new scientific classifications of bituminous coals.     

Coal as a source rock for oil: a review

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.     

显微组分大分子结构演化差异性及其动力学机制——研究进展与展望

显微组分物理化学性质是影响煤炭清洁高效利用和煤储层物性的重要因素,已经认识到决定显微组分性质的根本原因在于其大分子结构.为了揭示显微组分大分子结构演化特征及其控制因素,从显微组分大分子化学结构与物理结构、大分子结构演化的构造应力效应、煤变质全阶段大分子结构演化特征等方面,总结了国内外研究进展,分析了存在的不足.指出由于...     

试论等变质煤镜质体性质差异之普遍性

选择了不同地区和时代的不同变质程度的5个系列的煤样,对分离富集的镜质体主要特征进行了比较研究。研究发现:按海相和陆相划分,属同一相的不同时代的等变质煤的镜质体性质仍有差异,有些甚至相当明显。这表明,等变质煤镜质体性质存在的差异具有普遍性,并且其成因不止有煤相一个因素。      

Influence of particle and surface quality on the vitrinite reflectance of dispersed organic matter: Comparative exercise using data from the qualifying system for reflectance analysis working group of ICCP

The development of a qualifying system for reflectance analysis has been the scope of a working group within the International Committee for Coal and Organic Petrology (ICCP) since 1999, when J. Koch presented a system to qualify vitrinite particles according to their size, proximity to bright components and homogeneity of the surface. After some years of work aimed at improving the classification system using photomicrographs, it was decided to run a round robin exercise on microscopy samples. The classification system tested consists of three qualifiers ranging from excellent to low quality vitrinites with an additional option for unsuitable vitrinites. This paper reports on the results obtained by 22 analysts who were asked to measure random reflectance readings on vitrinite particles assigning to each reading a qualifier. Four samples containing different organic matter types and a variety of vitrinite occurrences have been analysed. Results indicated that the reflectance of particles classified as excellent, good or poor compared to the total average reflectance did not show trends to be systematically lower or higher for the four samples analysed. The differences in reflectance between the qualifiers for any given sample were lower than the scatter of vitrinite reflectance among participants. Overall, satisfactory results were obtained in determining the reflectance of vitrinite in the four samples analysed. This was so for samples having abundant and easy to identify vitrinites (higher plant-derived organic matter) as well as for samples with scarce and difficult to identify particles (samples with dominant marine-derived organic matter). The highest discrepancies were found for the organic-rich oil shales where the selection of the vitrinite population to measure proved to be particularly difficult. Special instructions should be provided for the analysis of this sort of samples. The certainty of identification of the vitrinite associated with the vitrinite reflectance values reported has been assessed through a reliability index which takes into account the number of readings and the coefficient of variation. The same statistical approach as that followed in the ICCP vitrinite reflectance accreditation program for single seam coals has been used for data evaluation. The results indicated low to medium dispersion for 17 out of 22 participants. This, combined with data from other sets of comparative analyses over a long period, is considered an encouraging result for the establishment of an accreditation program on vitrinite reflectance measurements in dispersed organic matter.     

应用高分辨率透射电镜研究煤显微组分的结构

应用高分辨率透射电镜研究变质系列镜质体和丝质体以及热解碳的物理结构特征表明,随煤级增高,镜质体的基本结构单元(BSU)的平均长度及缩聚芳香层平均环数NC呈增加的趋势;衍射环数增多,环的弥散程度减小,最终出现弧状;表明镜质体的BSU在变质过程中长大,定向性增强,VRo,max=6.50％是阶跃点,当VRo,max>6.50％,BSU突然定向排列。获得了很难获得的低煤化烟煤(VRo,max=0.66％)的高分辨图像,它的BSU尺寸小,无序排列。对丝质体和热解碳高分辨图像的首次研究发现,前者有序性差,随煤级演化的速度较镜质体慢,后者有序性好。     

实验变形煤结构演化的电子顺磁共振研究

通过１４件高温高压实验样品及其原样的电子顺磁共振研究,论述了温度、压力、应力、应变速率和应变强度等是影响变形煤化学结构演化的重要因素,但在不同的煤级中和不同的实验条件下,各因素所起的作用是不同的。变形煤ＥＰＲ参数的演化与镜质组反射率的变化密切相关,并且具有较好的规律性。说明镜质组反射率是煤化学结构演化的外在反映,是煤田构造研究中极为重要的标志物之一。     

Observations on Indian Permian Gondwana Coals Under Fluorescence Microscopy: An Overview

Macerals like sporinite, cutinite, suberinite and resinite of the liptinite group have been insufficiently recorded in Indian Permian Gondwana coals, until the fluorescence microscopy came into existence. With the introduction of this technique, macerals like bituminite, fluorinite and exsudatinite were convincingly recognized and alginite and liptodetrinite, normally mistaken for mineral matter under normal reflected light in routine coal petrographic analysis, were identified with certainty. Thus, fluorescence microscopy has added certain new macerals to the tally of the liptinite group and has increased their overall proportion in Indian Gondwana coals.In addition to the liptinite group, collodetrinite (=desmocollinite) and a certain fraction of collotelinite (=telocollinite) macerals of the vitrinite group were found to be fluorescing with dull reddish-brown to dark brown colours. Certain semifusinite and inertodetrinite macerals of inertinite group were also found to fluoresce with almost identical intensity and colour as that of the associated perhydrous (fluorescing) vitrinite. Contributions of degraded resinite, algal matter and bitumen in the formation of perhydrous vitrinite have been established. The fluorescence behaviour of inertinite appears to be related with its genesis from partial oxidation of resin/bitumen-impregnated cell walls.     

变形煤镜质组反射率演化的地化机理及其地质意义

通过X射线衍射(XRD)、电子顺磁共振(EPR)和核磁共振(NMR)等方法深入探讨了高温高压实验和构造煤样的化学结构演化特征,阐明了变形煤镜质组反射率的变化是其微观化学结构演化的外在反映。变形煤镜质组反射率的演化又受到应力和变形环境等因素的深刻影响,其真实地记录了构造变形历史中应力作用和应变环境等特征,是进行煤田构造研究的重要标志物之一      

Characterization of coal maceral concentrates by curie-point pyrolysis mass spectrometry

A set of 30 maceral concentrates consisting of 5 exinites (sporinites), 14 vitrinites and 11 inertinites (fusinites and semifusinites) was analyzed by Curie-point pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis techniques. Seventeen samples, representing sink/flotation concentrates of 7 different coals, were obtained through the British National Coal Board, whereas the remaining samples represent cesium-chloride density-gradient centrifugation fractions of two different U.S. coals prepared at the University of Utah.It is found that vitrinites, (semi)fusinites and, to some extent, sporinites show qualitatively similar rank-related changes, such as a decrease in dihydroxybenzene signals and an increase in napthalene signals with increasing rank. In fact, the overall pyrolysis MS patterns of inertinities show a close similarity to those of vitrinites of corresponding carbon content (as obtained from higher rank coals).Notwithstanding these similarities, however, the presence of basic differences in maceral structure is indicated by relatively minor but characteristic peak series in the liptinite (sporinite) as well as inertinite samples. Whereas inertinite spectra show relatively pronounced peak series at the high mass end of the spectrum which can be tentatively identified as representative of polynuclear aromatic compounds, sporinites are characterized by series of branched aliphatic and/or alicyclic polyenic hydrocarbons, possibly representing isoprenoids and related biomarker compounds.     

豫北煤田焦作、鹤壁、安阳矿区二1煤层优势断裂构造地球化学特征

对豫北煤田焦作、鹤壁和安阳矿区二１煤层的对比样（构造煤和原生结构煤）进行了显微镜和扫描电镜下观察、镜质组反射率测试、Ｘ射线衍射分析和化学分析等。研究结果表明,构造煤因发生了断裂构造地球化学作用,其化学成分、元素成分和煤分子结构与原生结构煤明显不同：构造煤的挥发分含量（％）比原生结构煤一般要小０．５５～３．４８,平均要小１．５９;构造煤和原生结构煤相比,碳含量（％）平均增加了３．１,氢含量（％）平均     

Secretinite—reflectance and chemical data from two high volatile bituminous coals (Upper Carboniferous) of North America

Secretinite—a maceral of the inertinite group as recognized by the ICCP in 1996—is a noncellular maceral of seed fern origin. New reflectance data indicate that this maceral has primary anisotropy with bireflectances of 0.4% to 0.9% in high-volatile B bituminous (Ro=0.6%) Carboniferous coal of North America. The highest reflectance is in cross-section as opposed to longitudinal section. Characteristic feature of secretinite is the virtual absence of Si and Al, unlike that in associated vitrinite. This indicates the absence of submicron aluminosilicates in secretinite and their presence in vitrinites. Secretinite is highly aromatic as indicated by low O/C ratios and high contribution of aromatic hydrogen bands detected by FTIR analysis.