Gelification of victorian tertiary soft brown coal wood. II. Changes in chemical structure associated with variation in the degree of gelification

The gross chemical structures of xylites and gelified soft brown coal woods, Latrobe Valley, Victoria, Australia, as determined by solid state nuclear magnetic resonance spectroscopy, are compared with those of present-day wood-derived materials prepared from an angiosperm, Eucalyptus regnans, and a gymnosperm (conifer), Pinus radiata. Also examined are the changes in the gross chemical structures of soft brown coal woods with increase in their degree of gelification and the relationship between these changes and variations in their chemical composition and microscopic appearance.The Victorian xylites exhibit greater affinities with the present-day gymnosperm than the present-day angiosperm. The progressive removal of cellulose with increasing degree of gelification can be equated with an increase in huminite reflectance, elimination of humotelinite autofluorescence and changes in the relative proportions of the humotelinite submacerals. The lignin structure of xylite is also modified during the gelification process, including the progressive loss of methoxyl groups and evidence of minor oxidation.     

Doppleritization of xylitic coal in the light of petrographic and chemical investigations

The paper presents the results of petrographic and chemical investigations of xylitic coal, xylite and their ash. As is known, a xylitic coal has the function of a lithotype whereas xylites are inclusions brown coals only. All these xylites were arranged according to the increasing degree of doppleritization of xylem in the sequence: common xylite, poorly, moderately and intensely doppleritized varieties, dopplerite coal. The distinctive criteria were their differentiated physical properties, which are also reflected in the variable petrographic and chemical compositions. The petrographic differences result from the replacement of textinite by ulminite and gelinite, while the differentiation of the chemical constitution is due to the increasing carbon content and the increasing number of functional groups that determine the aromatic nature of the internal structure of the coal. Infrared absorption spectroscopy, Raman spectroscopy and chemical analysis of ash have shown that the aromatization of coal and the resulting increase in the degree of order of the structural unit are due to the formation of organomineral compounds in the course of doppleritization. It appears from the investigations that the doppleritization of vegetable matter gives rise to gels that are a mixture of organo-mineral humic compounds. The process of humification leads to the formation of gel made up of humins. It follows then that there are two ways of initial coalification of plant material, both referred to as biochemical gelification.     

ON CLASSIFICATION AND NOMENCLATURE OF COAL MICROCOMPONENTS FOR TECHNOLOGICAL PURPOSES

A new classification of coal microcomponents based on microscopic features observable in reflected light is suggested. Primary basis of classification is nature of the original matter, namely its botanical nature and degree of coalification; and secondly on the degree of primary oxidation. According to the degree of coalification (“gelification” of the writer) distinguishes non-gelified partly gelified, and gelified substances; from the point of view of their botanic nature - woody, parenchyma and cortex tissues (also lipoids and algae) and, according to the degree of primary oxidation, four stages are indicated. In contrast to some existing classifications the writer does not recognize groups of gelified [anthraxylon?] and fusain microcompolents opposite to each other because he thinks that gelified components may later become fusained as well (as a result of oxidation). The writer underlines the importance of the microcomponents under consideration for practical purposes. — M. Russell     

Relations of petrographical and geochemical parameters in the middle Miocene Lavanttal lignite (Austria)

Samples from two lignite seams (Lower Seam, Upper Seam) of the Lavanttal basin (Austria) and additional xylite were investigated for variations in maceral composition, petrography-based facies indicators, bulk geochemical parameters, and molecular composition of hydrocarbons. Both seams originated in a topogenous mire and evolved within a transgressive setting. The final drowning of the mire is indicated by sapropelic shales. Whereas the sapropelic shale overlying the Lower Seam was deposited in a freshwater lake, the sapropelic shale above the Upper Seam represents a brackish lake.Numerous relationships are found between petrography-based facies indicators and the geochemical composition of organic matter. The contents of macerals of the liptinite group are positively correlated with soluble organic matter (SOM) yields and hydrogen index (HI). Consistent with maceral composition and high HI values, enhanced proportions of short-chain n-alkanes, which are predominantly found in algae and microorganisms, are obtained from samples of the sapropelic shales. The final drowning of the mire is reflected by decreasing pristane/phytane ratios, due to the rise in (ground)water table and the establishment of anaerobic conditions, as well as by decreasing ratios of diasterenes/sterenes, indicating increasing pH values in the mire. The degree of gelification of plant tissue (gelification index) is governed by the microbial activity in the mire, as indicated by the hopanes concentration. The differences in floral assemblage during the formation of the Lavanttal lignite seams are reflected by major differences in tissue preservation. Preservation of plant tissue (TPI) in the Lavanttal lignite is obviously controlled by the presence/absence of decay-resistant gymnosperms in the peat-forming vegetation, and additionally influenced by the relative contribution of wood to coal formation. The results provide evidence that valuable information for coal facies characterization could be obtained by petrography-based and geochemical facies indicators. An influence of the floral assemblage (gymnosperms/angiosperms ratio) and of the contribution of algal biomass on carbon isotopic composition of the organic matter (δ¹³C = − 24.2 to − 28.6‰) is proposed. Carbon cycling during biogeochemical decomposition of plant tissue by bacteria is suggested to affect the δ¹³C values of the coal. The chemotaxonomical classification of the xylites as gymnosperm remnants, based on the molecular composition of terpenoid biomarkers, is corroborated by the carbon isotopic composition of the xylites (mean δ¹³C = − 24.1‰) and the extracted cellulose (mean δ¹³C = − 20.2‰). The higher isotopic difference of about 3.9‰ between cellulose and total organic carbon of the xylites, compared to the difference between cellulose and wood found in modern trees, is explained by the smaller effect of decomposition on δ¹³C of cellulose.     

Effect of maceral subtypes and mineral matrix on measured reflectance of subbituminous coals and dispersed organic matter

The variability in reflectance of huminite (texto-ulminite, eu-ulminite A and B, different types of corpohuminite) and liptinite groups of macerals in subbituminous coals was examined using reflected light microscopy. All macerals were selected from coal and interbedded carbonaceous shale and carbonate sediment samples from the 515-m-thick coal deposit No. 2 located in the Hat Creek valley of south-central British Columbia. The measurements obtained reveal that, in addition to burial depth, reflectance distribution depends on maceral subtypes and associated mineral matrix.Huminite in the coals and sediments (kerogen) consists mainly of humotelinite, with eu-ulminite B being the dominant maceral sub-type. Reflectance values determined on huminite in coals and Type IIIb kerogen increase from eu-ulminite A and phlobaphinite type 1 through eu-ulminite B and phlobaphinite type 2 to gelinite. The reflectance of all five huminite maceral subtypes studied increases with depth. However, the increase of phlobaphinite type 1 and gelinite reflectance with depth is irregular.A comparison of the reflectance values obtained for the same maceral subtype (eu-ulminite B) from the interbedded coal, shale and carbonate samples records consistent differences, implying some dependence of the reflectance (and perhaps rate of organic maturation) on the mineral matrix. Generally, the highest eu-ulminite B reflectance was recorded from carbonate rocks and the lowest from shale, whereas coal matrix produced intermediate values.At present, it is not known whether differences in reflectance of eu-ulminite found in the above lithologies are due to differential retention, efficiency of reaction products removal, thermal conductivity of the lithologies, or existence of a calcium carbonate catalyst.     

Chemical structural models for coalified wood (vitrinite) in low rank coal

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.     

Sorption of methane on lignite from Polish deposits

Coal samples from Miocene lignite deposits (ortholignite—ECE-UN 2002) in Belchatow, Adamow, Konin and Turow (Poland) were analyzed to determine the relationships between coal properties and gas capacity.Investigations presented here addressed the occurrence of methane sorbet in lignite deposits within Poland's largest penetrated lignite deposits (e.g., Belchatow, Adamow, Turow and Konin).Lignite samples collected from surface mines were detritic coal with variable contents of xylites. The highest level of xylites (up to 25 vol.%) was found in carbon samples taken from the Belchatow deposit. Samples from other mines contained no more than 10 vol.% xylites. Petrographic compositions were dominated by huminite group macerals (73-88 vol.%) with atrinite, densinite and texto-ulminite, a porous form of ulminite; inertinite groups were less important components (4-8 vol.%).Isotherms were determined for methane sorption at 298 K with test pressure ranges below 1.2 MPa. At a pressure of 1.0 MPa, the largest gas capacity of approximately 1.7 [dm³ STP/kg] was found in the sample from Belchatow. This result may have been attributable to differences in the porosity of the samples; the porosity of the sample from Belchatow was twice as high as the porosities of the other coal samples. This variation in porosity resulted from the lithologic and maceral composition of the coal sample that contained substantial quantities of porous textinite and texto-ulminite.The thermal sorption equation was used to determine the limiting values of isosteric enthalpy of sorption, which suggested weak interactions between methane and the lignite matrix. The residual gas capacity of the tested samples was also determined.All samples exhibited a high residual methane-bearing capacity, which may not only cause methane to be released from coal at a pressure of 1 bar but also may pose a gas risk during mining operations.     

Coalification of organic matter in coal balls of the Pennsylvanian (upper Carboniferous) of the Illinois Basin, United States

An evaluation was made of the degree of coalification of two coal balls from the Illinois Basin of the Pennsylvanian (upper Carboniferous) of the United States. Previous interpretations are mainly misleading and contradictory, primarily because of the assumption that the brown color and exceptional cellular and subcellular preservation typical of American coal balls imply chemical preservation of cellulose and lignin, the primary components of peat. Xylem tissue from a medullosan seed fern contained in a coal ball and the coal attached to the coal ball from the Calhoun coal bed, Mattoon Formation, Illinois, was analyzed by elemental, petrographic, and nuclear magnetic resonance (NMR) techniques to determine the degree of coalification. The NMR and elemental data indicate the lack of cellulose and lignin and a probable rank of high-volatile C bituminous coal. These data corroborate data for a coal ball from the Herrin (No. 6) coal bed (Carbondale Formation, Middle Pennsylvanian) and support our hypothesis that the organic matter in coal balls of the Pennsylvanian strata of the United States is coalified to about the same degree as the surrounding coal. Data presented show a range of lower reflectances for xylem tissue and vitrinite in the analyzed coal balls compared with vitrinite in the attached coal.The data reported indicate that physical preservation of organic matter in coal balls does not imply chemical preservation. Also our study supports the hypothesis that compactional (static load) pressure is not a prerequisite for coalification up to a rank of high-volatile C bituminous coal.A whole-rock analysis of the Calhoun coal ball indicates a similarity to other carbonate coal balls from the United States. It consists primarily of calcium carbonate and 1–2% organic matter; silica and alumina together make up less than 0.5%, indicating the lack of minerals such as quartz and clays.     

Depositional environment and coal petrology of citak (akhisar) lignite deposits,west turkey

The Miocene alluvial, fluvial and lacustrine deposits occurring to the east of Akhisar (West Turkey) contain an economically potential lignite layer. This Miocene sequence is divisible into five formations, of which the Yeniköy Formation contains an autochthonous lignite horizon in its uppermost part. The Yeniköy Formation consists of, in a broadly ascending order, cross-bedded sandstones, channel-fill conglomerates, algal limestones, mudstones and carbonaceous shales. The Küçükderment Formation, which overlies the Yeniköy Formation and is composed of calcareous shale, clayey limestone, mudstone and bituminous shale, is of apparently lacustrine origin.The lignite horizon changes in thickness from 0.5 to 5 m, and is variably interbedded with clay and mudstone. It has an average calorific value of 13419 kJ/kg. The average moisture, ash and sulphur contents are 20%, 14% and 3%, respectively. Petrographic analysis indicates that the lignite samples consistently contain large amounts (more than 90%) of huminite (humocollinite, humodetrinite) and small amounts of intertinite (fusunite, semifusunite) and liptinite (resinite, sporinite, alginite). Average huminite/vitrinite reflectance ranges from 0.34 to 0.38%. In the DIN coal classification the rank features indicate “dull brown coal”.Macerals in the lignites indicate that the coal-forming peat accumulated in a predominantly forest-moor swamp environment in which reducing and low pH conditions prevailed. Spore and pollen assemblages suggest that a subtropical and humid climate existed during deposition of the coal.     

Paleomires of Eocene lignites of Bhavnagar,Saurashtra basin (Gujarat), western India: Petrographic implications

The Tertiary basins of Gujarat have always been a potential target for their hydrocarbon resources. The lignite resources of the region have also been an important field of research. The present paper presents the results of the petrological study carried out on the lignites of the Saurashtra basin. For this purpose samples were collected from lower and upper lignite seams from the Surkha lignite mine of Bhavnagar, Saurashtra. These samples were subjected to detailed petrographic analysis (both maceral and microlithotype). The study reveals that these lignites are dominantly composed of huminite group macerals while liptinite and inertinite group macerals occur in subordinate amounts. These lignites have attained a thermal maturity up to 0.28-0.30 percent vitrinite reflectance (VRr) which classifies them as ‘low rank C’ coals. Moreover, Bhavnagar lower lignite seam shows relatively less gelification as compared to the upper seam which suffered relatively more biochemical degradation. These lignites are characterized by high gelification index (GI) and low tissue preservation index (TPI).With the help of petrography based facies models an attempt has been made to reconstruct the environment of the paleomire of these lignites.     

Fluorescing macerals from wood precursors

A preliminary investigation into the origin of wood-derived macerals has established the existence of autofluorescent maceral precursors in the secondary xylem of swamp-inhabiting plant species. The optical character and fluorescent properties of microtomed thin-sections of modern woods from the Florida Everglades and Okefenokee Swamp, Georgia are compared to the character and properties of their peatified equivalents from various Everglades and Okefenokee peat horizons and their lignitic equivalents from the Brandon lignite of Vermont and the Trail Ridge lignitic peat from northern Florida. The inherent fluorescence of woody cell walls is believed to be caused by lignin though other cell wall components may contribute. The fluorescence spectra for several wood and cell types had a λ_max of 452 nm and Q value of 0.00. The color as observed in blue light and the spectral geometry as measured in UV light of peatified and lignitic woody cell walls (potential textinites) may change progressively during early coalification. Cell wall-derived maceral material is shown to maintain its fluorescing properties after being converted to a structureless material, perhaps a corpohuminite or humodetrinite precursor. Fluorescing xylem cell contents, such as condensed tannins or essential oils, can maintain the fluorescent character through early coalification.Xylem cell walls and xylem cell contents are shown to provide fluorescing progenitor materials which would not require subsequent infusion with “lipid” materials to account for their fluorescence as phytoclast material or as macerals in coal.     

Some inter-relationships of kerogen and humic acid fractions in the Victorian brown coal pale lithotype

The structural relationship between the kerogen, humic acid and solvent extractable acid fractions in a Victorian brown coal pale lithotype have been examined by IR, solid state ¹³C-NMR, elemental analysis and pyrolysis-gas chromatography. The solvent extractable acids and the kerogen fractions are highly aliphatic which is somewhat unusual, whereas the humic acids are composed substantially of phenolic constituents of probable lignin origin. This coal lithotype is an unusual low rank coal because of its high humic acid content. Its repeated occurrence over the limited depth profile examined here precludes a variation in coalification effects. The data suggest independent biological origins for the humic acid and kerogen fractions, and at the current level of maturation, the humic acid to kerogen transformation is little advanced in the pale lithotype. The kerogen is surprisingly aliphatic which suggests a more open marine (or lacustrine) environment than previously supposed.     

霍林河褐煤显微组分加氢液化性状的研究

对宏观煤岩类型和显微组分组成各不相同的5个褐煤煤样,进行了加氢液化和活化两组试验,通过对其转化率差别的分析,以及将活化后的残渣在普通显微镜、荧光显微镜和扫描电镜下的观察,了解了不同显微组分组和腐植组中的不同显微组分/亚组分/种的加氢液化特性和差别。这种差异表明显微组分组成不同的褐煤在加氢液化时的转化率不同,同时也显示了显微组分基本由腐植组组成的煤样转化率有差异。      

Organic petrology and geochemistry of the Carboniferous coal seams from the Central Asturian Coal Basin (NW Spain)

This paper presents for the first time a petrological and geochemical study of coals from the Central Asturian Coal Basin (North Spain) of Carboniferous (Pennsylvanian), mainly of Moscovian, age. A paleoenvironmental approach was used, taking into account both petrographic and organic geochemical studies. Vitrinite reflectance (R_r) ranges from 0.5% to 2.5%, which indicates a high volatile bituminous to semianthracite and anthracite coal rank. The coal samples selected for paleoenvironmental reconstruction are located inside the oil–gas-prone phase, corresponding to the interval between the onset of oil generation and first gas generation and efficient expulsion of oil. This phase is represented by coals that have retained their hydrocarbon potential and also preserved biomarker information. Paleodepositional reconstruction based on maceral and petrographic indices points to a swamp environment with vitrinite-rich coal facies and variable mineral matter content. The gelification index (GI) and groundwater influence index (GWI) indicate strong gelification and wet conditions. The biomarkers exhibit a high pristane/phytane ratio, suggesting an increase in this ratio from diagenetic processes, and a high diterpanes ratio. This, in turn, would seem to indicate a high swamp water table and a humid climate. The maximum point of coal accumulation occurred during the regressive part of the Late Moscovian sequence and in the most humid climate described for this period of time in the well-known coal basins of Europe and North America.     

The petrology of greek brown coals

Results are given in the petrography of Greek coals collected from most of the major coal-bearing basins in Greece.Rank was determined by measuring reflectances on the maceral varieties eu-ulminite A and eu-ulminite B and on the maceral textinite. Reflectances obtained from these components indicate a coalification stage of brown coal for all samples. Within this group of samples there is, however, a fairly wide scatter of reflectance values indicating for some of them the transition zone from peat to brown coal and for others a coalification stage close to the transition into bituminous coals. Reflectances obtained from eu-ulminite A and eu-ulminite B were found to correlate well with chemical rank parameters such as volatile matter and calorific value.Composition was determined by maceral analysis. The coals are in general characterized by low amounts of macerals of the inertinite group, low to intermediate amounts of macerals of the liptinite group and high amounts of macerals of the huminite group. Within the latter group densinite, attrinite, eu-ulminite and textinite make up the bulk of the samples.Typical macerals observed in the coals are illustrated by two black and white and three colour plates.Cluster analysis based on maceral distribution, mineral matter and reflectance indicates that the samples studied can be divided into three major groups. The first one is dominated by eu-ulminite and densinite with relatively high reflectances. The second is dominated by attrinite, textinite and texto-ulminite with somewhat lower reflectances. The third is represented by a single sample in which textinite and resinite are the most abundant macerals. This sample also has the lowest reflectance.     

A review of coal properties pertinent to carbon dioxide sequestration in coal seams: with special reference to Victorian brown coals

This paper presents reviews of studies on properties of coal pertinent to carbon dioxide (CO₂) sequestration in coal with specific reference to Victorian brown coals. The coal basins in Victoria, Australia have been identified as one of the largest brown coal resources in the world and so far few studies have been conducted on CO₂ sequestration in this particular type of coals. The feasibility of CO₂ sequestration depends on three main factors: (1) coal mass properties (chemical, physical and microscopic properties), (2) seam permeability, and (3) gas sorption properties of the coal. Firstly, the coal mass properties of Victorian brown coal are presented, and then the general variations of the coal mass properties with rank, for all types of coal, are discussed. Subsequently, coal gas permeability and gas sorption are considered, and the physical factors which affect them are examined. In addition, existing models for coal gas permeability and gas sorption in coal are reviewed and the possibilities of further development of these models are discussed. According to the previous studies, coal mass properties and permeability and gas sorption characteristics of coals are different for different ranks: lignite to medium volatile bituminous coals and medium volatile bituminous to anthracite coals. This is important for the development of mathematical models for gas permeability and sorption behavior. Furthermore, the models have to take into account volume effect which can be significant under high pressure and temperature conditions. Also, the viscosity and density of supercritical CO₂ close to the critical point can undergo large and rapid changes. To date, few studies have been conducted on CO₂ sequestration in Victorian brown coal, and for all types of coal, very few studies have been conducted on CO₂ sequestration under high pressure and temperature conditions.     

临沧超大型锗矿床的沉积环境、成岩过程和热液作用与锗的富集

临沧超大型锗矿庆的形成与其沉积、成岩和热液作用有密切联系。详细研究了矿床煤岩产出特征、煤岩组成、无机矿物、微量元素、腐殖体反射率,认为该矿床中的锗主要源于盆地西缘的白云母花岗岩的风化作用。在沉积作用阶段,锗被湖水中的低等生物和腐殖酸富集,为形成矿化煤打下基础。临沧褐煤经历了泥炭化阶段、早期成岩阶段和热液改造阶段。泥炭化阶段,沉积物中锗被凝胶体吸附和配合。早期成岩阶段,与腐残酸结合的锗,在碱性还原条     

Structural investigations of Australian coals II: A 13C-NMR study of the humic acids from Victorian brown coal lithotypes

The experimental conditions allowing quantitative interpretation of liquid state ¹³C-NMR spectra of the humic acids, derived from the five Victorian brown coal lithotypes are described. The structure of the two classes of humic acids investigated for each lithotype vary significantly in their level of aromaticity, the level of polar functional groups and aliphatic chains attached to their polyaromatic skeletons. Variation is also observed in the degree of aromaticity and oxygen-containing functions of humic acids with lithotype. These data are interpreted in the light of paleobotanical evidence, which suggests that the lithotypes represent variations in depositional environment and input to the coal seam.     

Lincang superlarge germanium deposit in Yunnan Province,China: Sedimentation,diagenesis,hydrothermal process and mineralization

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

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