The geochemistry of exinites—1. Evaluation of spectral fluorescence of a series of modern resins and fossil resinites

A series of six fossil resins and four modern resins have been analysed using microscope-based spectral fluorescence methods, in addition to a preliminary study of the chemical composition of these samples using infrared spectroscopy and pyrolysis-gas chromatography. This study illustrates problems encountered during the measurement of spectral fluorescence of resins and resinite kerogens using conventional microscopy methods. Most notable, alteration of fluorescence significantly influences spectral measurements. Further, fossilized resins within rocks are complex mixtures of resinite and bitumen. Pre-extraction of resinites prior to petrographic analysis resulted in somewhat more uniform spectral fluorescence results.Spectral fluorescence of recent resins used in this study could be used to distinguish angiosperm from gymnosperm derived resinite kerogens. Distinction of plant class source of resinite kerogens, however, is more difficult using this method and is considered genarally unreliable.     

Inside amber: New insights into the macromolecular structure of Class Ib resinite

Class Ib resinites are the most common subclass of amber and are found throughout the world. They have a macromolecular structure based on co-polymerized communic acid, communol and biformenes. Because this class of resinite does not contain succinic acid, crosslinking of the polymer through esterification of communol moieties has never been theorized. Analysis of Class Ib resinites from Grassy Lake and Cedar Lake in western Canada was performed using pyrolysis–gas chromatography–mass spectrometry with in situ hexamethyldisilazane derivatization, using a thermal separation probe to perform the pyrolysis and sample introduction. This has allowed larger, more complex fragments to be released from the polymer matrix than previously possible using instantaneous pyrolysis methodologies. The results show for the first time that Class Ib resinite can undergo self-crosslinking between the communol and communic acid moieties in the polylabdane matrix. The chromatographic results also show that a portion of the monoterpenes and non-polymerizable diterpenes in the resinite are bound to the polymer matrix and not fully occluded as was previously theorized. Fourier transform infrared (FTIR) spectra of the resinites are presented and a more accurate spectral interpretation is proposed, based on the chromatographic results.     

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.     

Class Id resinite from Canada: A new sub-class containing succinic acid

This paper describes a new sub-category of Class I resinites based on labdanoid diterpenes having an enantiomeric configuration, including ozic acid, ozol and enantio biformenes, and incorporating succinic acid. This hitherto unnamed resinite sub-class, now designated as Class Id, has been identified in three distinct deposits in Canada: two sites in Nunavut and one site in British Columbia. The composition of Class Id resinites was determined using pyrolysis-gas chromatography–mass spectrometry with in situ trimethylsilylation with hexamethyldisilazane, Py(HMDS)-GC–MS. Fourier transform infrared spectroscopy (FTIR) of the resinites was also carried out and provided evidence of partial esterification of the ozol with succinic acid.     

Tertiary deltaic and lacustrine organic facies: comparison of biomarker and kerogen distributions

Biological marker and kerogen compositional data in Tertiary deltaic and lacustrine settings were compared and contrasted. The two settings are represented by (a) coals and organic-carbon-rich shales in a ick deltaic sequence from the Far East, constituting three distinct organic facies, and (b) humic coals and spropelic oil shales in a restricted intermontane (freshwater) lacustrine sequence from western Montana (U.S.A.), constituting two distinct organic facies. Wedistinguish the organic facies in each depositional setting by systematic differences in gross compound class distributions, kerogen and infrared spectral characteristics, molecular character of pyrolyzates, sterane carbon number distribution and sterane/hopane ratios. The kerogens of the three deltaic organic facies are characterized by varying quantities of vitrinite, resinite, sporinite, cutinite and fluorescent amorphinite. Triterpane distributions reveal numerous terrigenous compounds, including oleanane, oleanenes and unidentified C₃₀ (presumably) resin-derived components. The two organic facies of the freshwater lacustrine setting are distinguishedased upon either a vitrinite or an alganite/fluorescent amorphinite predominance in the kerogen. Numerous characteristics facies-related markers are also present, including dehydroabietane (land plant resins) and 4-methylsteranes (perhaps from freshwater dinoflagellate input). The available molecular and petrographic data are evaluated, and characteristics are proposed for distinguishing five organic facies of these two depositional settings. The successful simultaneous use of molecular geochemistry and organic petrography in this study provides a format for refining the organic facies concept.     

ON MANGANIFEROUS FORMATIONS AND THE METALLOGENY OF MANGANESE,PAPER I. VOLCANOGENIC-SEDIMENTARY MANGANIFEROUS FORMATIONS

The article describes Carboniferous and Lower Liassic coal measures in Franz Josef Land, and a "2-ft coal bed" at the base of the Carboniferous motley sandstones observed by Fisher in Cook Cliffs at the south end of Prince George Land. Until recently the Cook Cliffs coal was identified by Dibner as "Paleozoic redeposited in Upper Triassic time." Later Dibner reassigned the coal and related beds to the Upper Triassic. Some doubt on this age is cast by the fact that the only coals on Spitzbergen are Lower Carboniferous. Ye. M. Andreyeva studied the coal's spores and found only Lower and Middle Carboniferous species. Traveling southeast of Wilczek Land in 1935, Yermolayev recovered coals he believed to be Paleozoic. Based on these finds, there is a strong likelihood of Paleozoic coals on Franz Josef Land. The Upper Triassic Vasil'yevsk Formation contains Noric to Rhaetic plants and spores. At Goristyy Cape (Champ Island) two brown coals occur; one is 1 m thick; 55 m higher is a 2-m bed coked at the top by an overlying basalt flow. The petrography of the coals is discussed. The Tegetthof Formation, based on its plant fossils, is Lower Liassic, compatible with sections on Spitzbergen. Next higher are Aalenian siltstones, Bathonian and sandy limestones with Volgian clams. Still higher are Lower Cretaceous volcanics with intercalated sandstones, shales and coals, divisible into the Tikhaya Cove Formation and Salisbury Formation. Altogether there are 13 coal beds in Franz Josef Land, ranging from Carboniferous up into the Lower Cretaceous (with 9 coal beds). Interesting petrographic details are included.—B. N. Cooper.     

Stratigraphic and regional variation of the petrographic and chemical properties of the Tradewater Formation coals and surrounding rocks in western Kentucky

The stratigraphic and regional variation of petrographic and chemical properties within the coals of the Upper Carboniferous Tradewater Formation and surrounding rocks in the Western Kentucky coal field were analyzed with the intent of constructing a depositional model for the occurrence of these low sulfur coals. Cores were megascopically described, and coal samples were analyzed for maceral, ash, and sulfur contents. These data were then analyzed to determine regional variation within the study area, as well as vertical variation within single coal columns.Sedimentological data from core logs indicate that the majority of the Tradewater rocks consist of irregularly distributed, coarsening-upward, fine-grained detrital material that was deposited in shallow bodies of water. Fossiliferous shales and limestones indicate a marine influence. Less common coarse-grained, fining-upward sequences appear to represent deposits of meandering or braided channels.Like the detrital rocks, the coal seams are irregularly distributed and exhibit substantial variation in petrographic and chemical properties which reflect changes in the Eh and pH of the coal swamp waters. These individual swamps were relatively limited in extent and probably occupied a low-lying coastal area. The relatively high vitrinite content of most of the coals suggests a reasonable degree of preservation of decaying plant materials. The study of benched samples from surface mines suggests a distinct dichotomy between swamps that were in more or less continuous contact with sulfate-rich marine or brackish water and those in which peat accumulated in a dominantly fresh-water setting. Most of the latter show a pattern of upward increasing sulfur content and decreasing vitrinite content, indicating increasing influences of oxygenated water that would encourage microbial action and which would degrade the peat and increase the tendency for sulfide precipitation. The high sulfur coals do not display this variability. The high rates of lateral variability encountered in the data suggest that future study should concentrate on smaller areas where variation can be completely documented.     

Petrological,chemical and depositional aspects of eastern Himalayan coals from elephant flat area,Kameng district,Arunachal Pradesh,India

The eastern Himalayan coals of India associated with Permian (Lower Gondwana) sediments in the Kameng district of Arunachal Pradesh have petrographic and chemical properties differing from Peninsular Permian coals.The coals are moderately to highly crushed and have reached a semianthracitic stage. Macerals are highly reflecting and homogenized. Vitrinite and inertinite exhibit a crushing effect in the form of criss-cross fissures and cracks. Exinite is unidentifiable and has attained an inertinitic reflectivity. The Kameng coals are of high rank with average fixed carbon 88.75% and volatile matter 13.75% on d.a.f. basis. The reflectance values (R_o-max 2.02–2.31% in oil) of these coals are quite high with marked anisotropy.It is inferred that these peculiar coal properties have been attained due to prolonged tectonic disturbance in the area during the later Himalayan orogeny. The coal characteristics suggest that these coals were formed in a humid tropical climate within a deltaic regime. The depositional site experienced occasional marine influx due to tectonically controlled subsidence during peat accumulation.     

河南省平顶山煤田晚石炭世太原组沉积环境和聚煤沉积特征

平顶山煤田的太原组属于混合型的碳酸盐浅海和陆源碎屑海岸沉积。下部和上部灰岩段主要形成于滨海潮间带和浅海中,并在其中发育行风暴浊流沉积。中部碎屑岩段为障壁岛-泻湖-潮坪体系沉积。太原组煤的显微组分为微镜惰煤,煤质属于低灰高硫煤。     

脆性变形序列构造煤纳米孔隙和粗糙度的原子力显微镜研究

煤孔隙结构是煤层气勘探开发与煤矿安全研究中的关键问题之一。构造煤相比于原生结构煤非均质性强,是煤储层研究中的热点和难点。采用原子力显微镜,结合NanoScope Analysis和Gwyddion分析软件,对脆性变形序列构造煤的孔隙结构和表面粗糙度特征进行研究。结果表明:构造作用整体上促进了脆性变形煤孔隙的发育,但不同脆性变形构造煤受构造作用影响的程度存在明显差异。根据煤受构造作用影响的程度,脆性变形煤孔隙结构演化可划分为强弱2个阶段:弱脆性变形阶段(原生结构煤—碎裂煤—片状煤—碎斑煤)构造作用对煤体的孔隙结构影响较小,平均孔数量缓慢增长,平均孔径缓慢减小,该阶段构造作用主要促进了100~200 nm大孔的发育;强脆性变形阶段(碎斑煤—碎粒煤—薄片煤)构造作用对煤体孔隙结构产生了显著影响,平均孔数量迅速增长,平均孔径迅速减小,这一阶段构造作用主要促进了10~50 nm介孔和50~100 nm大孔的发育。这表明脆性变形构造煤孔隙结构并非简单的线性演变。不同脆性变形煤的算术平均粗糙度和均方根粗糙度参数分别为3.00~6.05 nm和3.94~7.62 nm,其中,弱脆性变形阶段粗糙度整体较高且无明显变化,而强脆性变形阶段粗糙度迅速降低。通过AFM剖面分析,建立了煤表面孔隙形态的数学模型。基于该模型的算术平均粗糙度模拟结果表明,大孔是煤表面粗糙度的主要贡献者,构造作用主要通过影响煤中的孔隙结构,进而影响煤的表面粗糙度。      

Micro-FTIR spectroscopy of liptinite macerals in coal

Reflectance FTIR microspectroscopy has been used to investigate the chemical structure of the liptinite macerals, alginite, bituminite, sporinite, cutinite and resinite in bituminous coals of Carboniferous to Tertiary age. In comparison with the spectra of vitrinite in the same coals, the micro-FTIR spectra of liptinite macerals are characterized by stronger aliphatic CH_x absorptions at 3000–2800 and 1460–1450 cm⁻¹, less intense aromatic C=C ring stretching vibration and aromatic CH out of plane deformation at 1610–1560 and 900–700 cm⁻¹ respectively and various intense acid C=O group absorptions at 1740–1700 cm⁻¹. The peaks at 1000–900 cm⁻¹ due to aliphatic CH₂ wagging vibrations in olefins and at 730–720 cm⁻¹ due to CH₂ rocking vibration in long chain aliphatic substances ([CH₂]_n, n≥4), are characteristic of liptinite macerals. Collectively the micro-FTIR spectral characteristics indicate that liptinite is composed of greater numbers of long chain aliphatics, fewer aromatics and a broader range of oxygen-containing groups than other macerals. Marked differences exist in micro-FTIR spectra within the liptinite maceral group. Alginite has the strongest aliphatic and least aromatic absorptions followed by bituminite, resinite, cutinite and sporinite. The aliphatic components in alginite are the longest chained and least branched whereas those in sporinite are the shortest chained and most branched. Bituminite, resinite and cutinite are intermediate. Notable differences in micro-FTIR spectra of individual liptinite macerals, such as intensities and peak locations of aromatic C=C in alginite, C=O groups in bituminite and resinite and substituted aromatic CH and C–O–C groups in cutinite and sporinite, also exist, which are attributed to differences in depositional environments or biotaxonomy.     

Petrology of oligocene coal, makum coalfield, assam, Northeast India

There are five workable coal beds in the Tikak Parbat Formation of the Barail Group in the Makum coalfield, Tinsukia District, Assam. Two of these beds, 18 and 6 m thick, are persistent across the field. The coal is high volatile bituminous B/C, has excellent coking properties, and is of great importance as a blending coal to improve the coking properties of the lower-quality Gondwanan coals.These coals are bimacerites as vitrinertite or trimacerites as duroclarite. Virtrinite predominates with minor amounts of other macerals and minerals. The high percentage of vitrinite indicates that the bark and woody tissues were the dominant contributors to the precursor peat. These peats were strongly decomposed under anaerobic conditions as indicated by the abundance of the collinite type of vitrinite.     

The Abnormal Condition Analysis used to characterize weathered discard coals

Coal, by its nature, is unstable and weathers when exposed to moisture and oxygen. Weathering can result in a general decline on the commercial value and technological properties of coal. Coals of similar chemical properties have been shown to combust differently, and the differences can be attributed to petrographic composition variations, poor combustion environments, and weathered particles. Stockpiled and dumped discard coals have been targeted for use by a lower power utility, and a novel technique was developed to quantify and qualify the degree of weathering in these coals. The petrographic based Abnormal Condition Analysis (previously referred to as the Weathering Index Analysis) considers features not typically characterized during routine petrographic analyses, but which may have an impact on the technological properties of coals. Discard coals ranging in age from 5 to 40 years where characterized to determine the extent of secondary weathering. Eight secondary weathering features, clearly different from inherent weathering, were qualified and quantified. Margin effect appears to be an early microscopic indicator of weathering, followed by discoloration. Alteration minerals have only been observed in stockpiled and dumped coals and hence could be a useful feature to benchmark when considering whether or not a coal has been stored. Long-term stored coals have microcrack and fissure patterns clearly different from fresh coals. The length of exposure to weathering processes was determined to be proportional to the extent of weathering as determined petrographically. The Abnormal Condition Analysis should be used as a supplement to routine coal petrography as it can assist with the determination of anomalous behavior of coals.     

显微荧光光谱技术在油气成藏研究中的应用——以塔里木盆地巴什托上古生界油气藏为例

根据原油在紫外光的激发下产生荧光的特点,通过显微荧光光谱方法,对有机包裹体的荧光光谱进行定量化分析,利用其主峰波长与荧光强度、主峰波长与红/绿商的相关性,对塔里木盆地巴什托上古生界油气藏的成藏特征进行了初步研究。在研究区所采集的32块岩石样品中共获得64个荧光光谱数据。分析结果表明,巴什托上古生界油气藏存在3个油源,其主峰波长主要集中在439~443nm、469~472 nm和498~503 nm三个值段上,且为不同演化阶段的混源充注。前两者来自于寒武—奥陶系烃源岩,由下至上充注成藏;后一油源来自于石炭系巴楚组,随演化程度的变化同时向上、下两个方向充注。综合同期捕获不同主峰波长的有机包裹体,推测研究区至少存在4期油充注、1期天然气充注。     

Application of SAXS and SANS in evaluation of porosity, pore size distribution and surface area of coal

This paper discusses the applicability of small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS) techniques for determining the porosity, pore size distribution and internal specific surface area in coals. The method is noninvasive, fast, inexpensive and does not require complex sample preparation. It uses coal grains of about 0.8 mm size mounted in standard pellets as used for petrographic studies.Assuming spherical pore geometry, the scattering data are converted into the pore size distribution in the size range 1 nm (10 Å) to 20 μm (200,000 Å) in diameter, accounting for both open and closed pores. FTIR as well as SAXS and SANS data for seven samples of oriented whole coals and corresponding pellets with vitrinite reflectance (R_o) values in the range 0.55% to 5.15% are presented and analyzed. Our results demonstrate that pellets adequately represent the average microstructure of coal samples.The scattering data have been used to calculate the maximum surface area available for methane adsorption. Total porosity as percentage of sample volume is calculated and compared with worldwide trends. By demonstrating the applicability of SAXS and SANS techniques to determine the porosity, pore size distribution and surface area in coals, we provide a new and efficient tool, which can be used for any type of coal sample, from a thin slice to a representative sample of a thick seam.     

From in-situ coal to fly ash: a study of coal mines and power plants from Indiana

This paper presents data on the properties of coal and fly ash from two coal mines and two power plants that burn single-source coal from two mines in Indiana. One mine is in the low-sulfur (<1%) Danville Coal Member of the Dugger Formation (Pennsylvanian) and the other mines the high-sulfur (>5%) Springfield Coal Member of the Petersburg Formation (Pennsylvanian). Both seams have comparable ash contents (11%). Coals sampled at the mines (both raw and washed fractions) were analyzed for proximate/ultimate/sulfur forms/heating value, major oxides, trace elements and petrographic composition. The properties of fly ash from these coals reflect the properties of the feed coal, as well as local combustion and post-combustion conditions. Sulfur and spinel content, and As, Pb and Zn concentrations of the fly ash are the parameters that most closely reflect the properties of the source coal.     

Petrographic prediction of coking properties for the Curragh coals of Australia

Curragh Queensland Mining Limited, Australia, produces a high quality medium volatile bituminous coking coal from the Orion, Pollux and Castor seams from the upper Permian Rangal Coal Measures. It is one of the lowest ash, prime hard coking coal blends produced in Australia. It is also low in sulfur and produces very strong coke when carbonized alone and in blends. Early attempts to predict coking properties of the coals from petrographic data produced predicted coke stabilities that were significantly lower than those determined from coke tests. There is some question as to how much of the ‘inertinite’ in these and other southern hemisphere coals is truly inert during carbonization and how much is reactive. The current study characterized the Curragh coals in terms of physical, chemical and petrographic characteristics and also involved the production of test oven cokes for characterization and strength testing. As part of the work effort a series of suggested techniques for improving predictions of coke strength from petrographic data were examined and a new and improved technique was developed for the Curragh coals. How broadly the technique can be applied to other coals needs to be determined.     

Applications of microscopy to coke making

A Canadian perspective of the petrographic, thermal rheological and grade of metallurgical coals required to make coke with high strength and strength after reaction (CSR) properties is presented. The development of automated microscopic techniques to obtain reproducible and reliable petrographic data to predict coke quality is discussed. The amount of “altered vitrinite” in the microscopic coke textures has been used as a reference to quantifiy in situ coal oxidation. Relationships between coke microscopy, coal petrography and thermal rheological data show that FSI can be used to estimate the amount of oxidized vitrinite plus petrographic inert contents of coal. Plastic temperature ranges determined from microscopic examination of the coal/coke transformations for Appalachian and Canadian coals show that standard thermal rheological tests underestimate the plastic range for high inertinite coals.     

Classification and Potential Utilization of Eocene Coals of Meghalaya,North East India

In the present study, petrographic and geochemical investigation of Meghalayan coal deposits have been carried out to classify these coals in terms of rank, type and grade, using Indian and International classification schemes. Based on petrographic and geochemical characteristics, an attempt has also been made to identify the potential utilization of Meghalayan coals for various industrial applications. According to the study, these coals have been classified as sub-bituminous C to high volatile bituminous in rank, vitric in type and clean to ashy in grade. Considering their hydrocarbon potential, these coals are suitable for liquefaction and gasification.     

Petrographic properties of major coal seams in Turkey and their formation

Most types of coal in Turkey are generally low in rank: lignite, and subbituminous. Most of the coal was formed during the Miocene, Eocene, and Pliocene ages. There are only a few thin Jurassic-age coal occurrences in Turkey. Pennsylvanian age bituminous coal is found on the Black Sea coast. General implications of the petrographic properties of Turkey's coal seams and coal deposits have not yet been taken into consideration comparatively or as a whole.For this study, about 190 channel samples were collected from different locales. The composite profile samples of the seams were taken into considerations. The content and depositional properties as well as some chemical and physical properties of the main coal seams are compared. All coal samples tend to have similar coal petrographic properties and were deposited in intermontane lacustrine basins. Later, they were affected by faulting and post-depositional volcanic activity. As a result, there are variations in the properties and rank of the coal samples. The most abundant coal maceral group is huminite and the most abundant maceral is gelinite. The liptinite and inertinite contents of the coal are low and the maceral contents of the coals show great similarity. The depositional environments of the all coals are lacustrine dominated.