Chemical composition of macerals in bituminous coals of the Gunnedah Basin, Australia, using electron microprobe analysis techniques

The chemical composition of the organic matter in the principal macerals of high-volatile bituminous coals from the Gunnedah Basin, New South Wales (Rv_max of telocollinite between 0.6 and 1.1%) has been evaluated from polished section specimens using an electron microprobe technique. Highest proportions of carbon occur in the inertinite macerals, especially fusinite and secretinite (formerly resino-sclerotinite), as well as in sporinite; lowest proportions of carbon occur in the different macerals of the vitrinite group. Oxygen shows the reverse trend, being most abundant in vitrinite and least abundant in the inertinite components, whereas sulphur is lowest in the inertinites and highest in the liptinite (mainly sporinite) present. Evaluations of maceral composition, using the carbon content of telocollinite as a rank indicator, show that carbon is more abundant in both sporinite and semifusinite, relative to vitrinite, in low-rank high-volatile bituminous coals. The difference decreases with increasing rank, and the proportion of carbon in telocollinite becomes essentially the same as that in sporinite and semifusinite at carbon contents of about 89 and 91%, respectively. The carbon content of fusinite and secretinite, on the other hand, does not seem to vary appreciably with rank advance. No significant difference in composition occurs in the rank range studied between the three vitrinite varieties present, desmocollinite, telocollinite and a more highly reflecting telocollinite resembling pseudovitrinite. No evidence was found to indicate a higher hydrogen content, relative to telocollinite, for the vitrinite matrix of desmocollinite.     

Initial volatilization temperatures and average volatilization rates of coal — Their relationship to coal rank and other characteristics

Two thermal parameters, initial volatilization temperature (IVT) and average volatilization rate (AVR), have been determined by thermogravimetric analysis in argon for 38 coal samples ranging in rank from lignite to low-volatile bituminous. Both IVT and AVR are correlated with percent volatile matter and vitrinite reflectance.The IVT values increase gradually from about 250 to 445°C with increasing rank; however, a change in slope is observed in the region of high-volatile bituminous coals (from about 340°C to about 380°C) when IVT's are plotted against percent volatile matter or percent fixed carbon. The changes in slope near 340°C and near 380°C occur at “coalification jumps” recognized on the basis of changes in the optical and chemical character of the macerals. In general, AVR values decrease gradually with increasing rank for the lignite and sub-bituminous coals and for the medium- and low-volatile bituminous coals; however, a sharp increase in AVR occurs in high-volatile bituminous coals. The change in slope of the IVT curves and sharp increase in the AVR values for high-volatile bituminous coals reflect the development of new, higher vapor pressure organic compounds produced during this stage of the coalification process.A plot of AVR vs IVT reveals three regions which correspond to: (1) lignite and sub-bituminous coals; (2) high-volatile bituminous coals; and (3) medium- to low-volatile bituminous coals.     

Composition of soluble organic matter in coals: relation to rank and liptinite fluorescence

Study of a series of twenty-six German high volatile bituminous B to low volatile bituminous coals of Upper Carboniferous age by recently refined analytical methods (‘flow-blending’ extraction, medium pressure liquid chromatography, HPLC, glass capillary gas chromatography and spectral fluorescence microscopy) reveals that yield and composition of soluble organic matter are strongly controlled by rank. In particular, the following points of inflection are noted in rank trends around 0.9% vitrinite reflectance: a maximum in yields of total soluble organic matter, aromatic hydrocarbons and n-alkanes; the most pronounced change in aromatic hydrocarbon composition; a trend reversal for pristane/ phytane ratios; a gradient change in the odd/even-predominance of long chain n-alkanes; appearance of a bimodal n-alkane distribution; and a sharp drop in concentration of individual n-, and isoprenoid alkanes. This discontinuity in rank trends around 0.9% Rm is interpreted to reflect a major change in reaction types, i.e. a shift from predominantly hydrocarbon generating to predominantly fragmentation reactions. Rank trends of maceral fluorescence exhibit the following pronounced changes over a similar but broader rank range: Different types of the maceral sporinite show a relatively abrupt shift of the fluorescence colour from yellow towards red between 0.8–0.9% Rm while up to about 1.0% Rm a sharp increase is recorded in the proportion of fluorescent vitrinite. This coincidence at a near-equal rank stage suggests a common cause for changes in yield and composition of the soluble organic matter and the maceral fluorescence of these coals.     

Liquid hydrocarbon generation potential from Tertiary Nyalau Formation coals in the onshore Sarawak, Eastern Malaysia

Tertiary coals exposed in the north-central part of onshore Sarawak are evaluated, and their depositional environments are interpreted. Total organic carbon contents (TOC) of the coals range from 58.1 to 80.9 wt. % and yield hydrogen index values ranging from 282 to 510 mg HC/g TOC with low oxygen index values, consistent with Type II and mixed Type II–III kerogens. The coal samples have vitrinite reflectance values in the range of 0.47–0.67 Ro %, indicating immature to early mature (initial oil window). T _max values range from 428 to 436 °C, which are good in agreement with vitrinite reflectance data. The Tertiary coals are humic and generally dominated by vitrinite, with significant amounts of liptinite and low amounts of inertinite macerals. Good liquid hydrocarbons generation potential can be expected from the coals with rich liptinitic content (>35 %). This is supported by their high hydrogen index of up to 300 mg HC/g TOC and Py-GC (S ₂) pyrograms with n-alkane/alkene doublets extending beyond C₃₀. The Tertiary coals are characterised by dominant odd carbon numbered n-alkanes (n-C₂₃ to n-C₃₃), high Pr/Ph ratio (6–8), high T _m /T _s ratio (8–16), and predominant regular sterane C₂₉. All biomarkers parameters clearly indicate that the organic matter was derived from terrestrial inputs and the deposited under oxic condition.     

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.     

Petrographic variation in the Springfield (No. 9) coal in Western Kentucky

The Springfield (Western Kentucky No. 9) coal of the Carbondale Formation (Middle Pennsylvanian) in the Western Kentucky Coal Field of the Illinois Basin was sampled in eleven mines from one to three channels of three equal benches. The rank of the coal is high-volatile C bituminous in the Moorman Syncline and in the Henderson Basin and high-volatile B bituminous in the Webster Syncline. The percentage of total vitrinite macerals and of total vitrinite plus liptinite was found to decrease significantly from the bottom bench through to the top bench. In a comparison of the sources of variation within the set of maceral data it was found that the only significant variation in the vitrinite and vitrinite plus liptinite percentages was between the benches. Both the rank of the coal and the maceral percentages are varying in a predictable manner.     

Changes in hydrocarbon maturity indices with coal rank and type,Buller Coalfield,New Zealand

The Buller Coalfield (South Island, New Zealand) is an inverted late Paleogene Basin that contains middle Eocene bituminous coals which exhibit considerable variation in both coal rank (across-basin), and coal type (in-seam). Twenty-two fractionated bitumen extracts of Brunner Coal Measures coal samples from 12 drillholes were analyzed by GC and GC–MS to characterize the effect of coal rank and type on conventional hydrocarbon maturity indices at the beginning and end of the oil window (0.56–1.26% Ro_max).The Carbon Preference Index, pristane/phytane and isoprenoid/n-alkane ratios evolve throughout the high volatile bituminous B rank stage, while other biomarker ratios [18α(H)-22,29,30-trisnorneohopane/17α(H)-22,29,30-trisnorhopane (Ts/Tm), 18α(H),21β(H)-30-norneohopane (C₂₉ Ts)/17α(H),21β(H)-30-norhopane and C₃₀ diahopane/hopane] do not show appreciable change in value until medium volatile bituminous rank. Various aromatic based ratios appear to be more effective in delineating rank throughout the entire oil window; in particular the Methylphenanthrene Index and vitrinite reflectance are positively correlated over the entire bituminous rank range. However, subtle changes in depositional conditions (variable coal type) complicate these rank estimates. Within a given coal seam, variation in CPI, isoprenoid/n-alkane and hopane/sterane ratios appear to be related to the hydrogen content of the coal, while the homohopane index and the oleanane/hopane ratio covary with sulfur content. As with depressed vitrinite reflectance values, MPI is similarly lowered in the perhydrous samples. The mechanisms that control these hydrocarbon parameters during deposition and diagenesis are complex and convoluted, however, changes in bacterial activity and community (with marine incursion) appear to play an important role. Due to these anomalies, none of the hydrocarbon maturity indices calculated can be singularly used to constrain coal rank.     

Oil-generating potential of Tertiary coals and other organic-rich sediments of the Nyalau Formation,onshore Sarawak

The oil-generating potential of coals and other organic-rich sediments from the Late Oligocene–Early Miocene Nyalau Formation, the offshore extension of which is believed to be a major source rock, is evaluated. Coals of the Nyalau Formation are typically dominated by vitrinite, with moderate and low amounts of exinite and inertinite, respectively. Significant amounts of clay minerals are present in these coals and those containing between 15 to 65% mineral matter by volume are termed carbargilite. The samples analysed range from sub-bituminous to high-volatile bituminous rank, possessing vitrinite reflectance in the range 0.42% to 0.72%. T_max values range from 425°–450°C which is in good agreement with vitrinite reflectance data. Good oil-generating potential is anticipated from these coals and carbargilites with moderate to rich exinite content (15–35%). This is supported by their high hydrogen indices of up to 400 mgHC/gTOC, Py–GC (S2) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀, and their being in the early to mid-mature oil-window range. Petrographically, the most significant evidence of the oil-generating potential of these coals is the generation of petroleum-like materials (exsudatinite) visible under the microscope. Exsudatinite is a secondary maceral, commonly considered to represent the very beginning of oil generation in coal, which is shown here to also have an important role to play in hydrocarbon expulsion. The precursor of exsudatinite in these coals is the maceral bituminite which readily expels or mobilizes to hydrocarbon-like material in the form of oil smears and/or exsudatinite as observed under the microscope. The maceral bituminite is considered to play a major generative role via early exsudatinite generation, which is considered to facilitate the overall expulsion process in coaly source rocks.     

Hydrocarbons and fatty acids in the Evergreen Shale,Surat Basin,Queensland, Australia

Alkane hydrocarbon and n-fatty acid distributions have been examined in cores taken over a 550 ft thickness through the lower Jurassic, largely non-marine Evergreen Shale, Surat Basin, Queensland, Australia. No depth trends in compound abundances or carbon preference indices are discernible. There is no evidence for significant generation of n-alkanes from kerogen nor for cracking of long-chain n-alkanes. The present distribution patterns of the biochemicals probably reflect closely the nature of the original organic matter. The general strong dominance of long-chain (C₂₀₊) n-alkanes; the lack of evidence for diagenetic change; and the absence of correlation between abundances of n-alkanes and n-fatty acids (among both the longer- and shorter-chain compounds), lead to the conclusion that at least the long-chain n-alkanes were largely deposited as such in the sediment, having originated in land-plant material, remains of which are abundant in the samples. In the upper 170 ft. (possibly marine), n-alkanes with chain lengths below C₂₀ become important, suggesting greater significance of aquatic life as a source of organic matter at the time of deposition, a conclusion which is in general accord with the geological history of the basin, although this history is not well known.     

Tracing the origins of polymethylene moieties in coal

Many coals have been shown to contain long polymethylene segments (up to C₃₀ and longer) which crack to ethylene, propylene, butadiene and other low molecular weight hydrocarbons when the coals are pyrolyzed. The polymethylene content varies in different coals and can be 10% or more in low rank coals. Cannel coals may contain up to 20% polymethylene. Polymethylene moieties are either very low or absent in low-volatile bituminous coals and anthracite.A method of analysis for polymethylene in coals, based on liquefaction in a donor solvent followed by ¹H NMR spectroscopy has been described. With this analysis, it has been shown that polymethylene moieties are present in higher concentrations in exinite macerals than in vitrinites or inertinites. Analysis of peats also show the presence of polymethylene components at levels similar to that found in coal. Analysis of various parts of present-day plants also shows the presence of polymethylene materials in concentrations varying significantly from one kind of plant to another. Within a given plant type, some parts of the plant appear to be richer in polymethylene than others. Spores and pollen are frequently especially rich in polymethylene, accounting for the corresponding high concentration in exinite macerals in coal.Samples of Texas Eocene lignites representing a depositional time interval of 15–20 million years and three distinctly different climatic and vegetational conditions were analyzed for polymethylene contents. The differences in polymethylene levels are consistent with differences in flora and support the idea that the original plants are the sources of polymethylene components in coal.     

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.     

A quantitative fluorescence technique for evaluating thermal maturity: Instrumentation and examples

Fluorescence microscopy is useful not only for identifying most of the oil-prone organic matter (macerals) in sedimentary rocks and coals but also for assessing their thermal maturities (ranks). This report introduces a violet-light excitation system which induces more than one order of magnitude stronger fluorescence intensity that the commonly used UV-light excitation system. The red/green quotient from violet-light excited fluorescence, Q_v, of sporinite can be easily measured using this system. Several examples using coal and cuttings samples are presented to demonstrate the use of this technique for evaluating the thermal maturities of coals and sedimentary rocks.From the results of our studies we conclude that:

• 1.(1) Violet-light excited fluorescence from sporinites can be routinely measured to assess thermal maturity.
• 2.(2) Spectral (Quantitative) fluorescence technique is useful for evaluating thermal maturity when samples are poorly polished or deficient in vitrinite.
• 3.(3) Visual (Strew-mounted) kerogen slides can not be used for fluorescence measurements unless a non-fluorescent mounting medium is used.

     

Fossil fuel compounds from fly dust in recent organic matter of southern Poland peats

Several samples of peat from 6 bogs located in southern Poland were investigated for occurrence and distribution types of biomarkers present in their extractable organic matter fraction. It was found that there are inputs from two different sources of organic compounds differing in their characteristics and origin: (1) recent immature peat organic matter deposited in situ which is the source of all polar functionalized compounds, most of n-alkanes, and acyclic isoprenoids, and (2) mature fossil fuels, most probably bituminous coals from the Upper Silesia Coal Basin of vitrinite reflectance equivalent values of 0.9–1.1%. The latter compounds were most probably transported with fly ash to bogs from nearby settlements utilizing such fuel in domestic ovens. This group includes pentacyclic triterpenoids (hopanes and moretanes), minor amounts of n-alkanes, and numerous alkyl naphthalenes and alkyl phenanthrenes. All these compounds show distributions and values of geochemical ratios characteristic for mature organic matter confirming there ex situ origin.     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.     

Determination of rank and petrographic composition of Jurassic coals from eastern Surat Basin,Australia

Petrographic analysis and rank determination were carried out on coals from a Jurassic sequence in eastern Surat Basin, Australia. The coals consist mainly of exinite-rich clarite, with desmocollinite as dominant maceral of the vitrinite group. Petrographically there is no significant variation in the composition of the coals. A herbaceous swamp type, free from severe oxidation/ dehydration, appears to have been a dominant depositional environment during the peat accumulation.The coal rank ranges from sub-bituminous B to high-volatile bituminous C/B. Vitrinite reflectance/ depth profile shows a uniform increase in coalification with depth of burial.     

The rank evaluation of South Brazilian Gondwana coals on the basis of different chemical and physical parameters

Rank evaluation of South Brazilian Gondwana coals according to the American (American Society for Testing and Materials, ASTM) and German (Deutsche Industrie Normen, DIN) standard specifications or on the basis of Alpern's Universal Classification has too often led to conflicting results.When any attempt is made to determine the rank of Brazilian coals by using methods established for the Northern Hemisphere coals, two sorts of difficulties arise: namely, (1) the reflectence measurements do not indicate the real degree of coalification of the organic matter because of the liptinitic impregnations of the vitrinites, and (2) random reflectance values (R_ran, moisture, volatile-matter and carbon contents as well as the calorific value do not correlate when plotted on the ASTM and DIN classification schemes.In addition, when rank determinations are carried out by using fluorescence measurements and geochemical analyses the results are at variance in relation to those determined by the conventional chemical and physical parameters.It is suggested that the rank evaluation of South Brazilian coals is far more meaningful if carried out by reflectance measurements on vitrinites along with fluorescence measurements on sporinites, alginites and coal extracts.     

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.     

Some chemical structural features of coals of differing maceral distributions and stratigraphy

Six North American bituminous coals (four Carboniferous and two Cretaceous) and eight maceral concentrates from Carboniferous British seams have been heated with tetralin and hydrogen to 400°C. The hexane-soluble parts of the products were separated by column chromatography and the fractions were then analyzed by gas chromatography/mass spectrometry. In all cases the aromatic hydrocarbon fraction was a very complex mixture containing a number of alkylated biphenyls, diphenylmethanes and -ethanes, and polycyclic compounds. However single ioncchromatography (m/z = 142) showed that, in addition to these, the products from five of the six American coals contained homologous series of long chain n-alkylnapththalenes with alkyl groups extending to C₁₆. In other fractions from the American coals, homologous series of n-alkylfurans and alkylphenols were found to be major components, as also were many alkylcyclohexenones related to isophorone. Extensive homologous series of n-alkyl aromatics were not detected in products from any of six vitrinites from British seams, though series of n- and iso-alkylphenols were found in the products from two sporinite concentrates. A number of polycyclic ketones apparently related to sterols were found in the products from the British vitrinites but not from any American coals. Reasons for what appear to be systematic structural differences between the American and British coals are discussed. Differences in stratigraphy are noted and it seems not impossible that differences in source vegetation are significant.     

Petro-chemical investigation of some perhydrous Indian coals

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.     

Role of coal type and rank on methane sorption characteristics of Bowen Basin, Australia coals

The effect of coal composition, particularly the organic fraction, upon gas sorption has been investigated for Bowen Basin and Sydney Basin, Australia coals. Maceral composition influences on gas retention and release were investigated using isorank pairs of hand-picked bright and dull coal in the rank range of high volatile bituminous (0.78% R_{o max}) to anthracite (3.01% R_{o max}). Adsorption isotherm results of dry coals indicated that Langmuir volume (V_L) for bright and dull coal types followed discrete, second-order polynomial trends with increasing rank. Bright coals had a minimum V_L at 1.72% R_{o max} and dull coals had a minimum V_L at 1.17% R_{o max}. At low rank, V_L was greater in bright coal by about 10 cm³/g, but as rank increased, the bright and dull trends converged and crossed at 1.65% R_{o max}. At ranks higher than 1.65% R_{o max}, both bright and dull coals followed similar trends. These competing trends mean that the importance of maceral composition on V_L varies according to rank. In high volatile bituminous coals, increases in vitrinite content are associated with increases in adsorption capacity. At ranks higher than medium to low volatile bituminous, changes in maceral composition may exert relatively little influence on adsorption capacity. The Langmuir pressure (P_L) showed a strong relationship of decreasing P_L with increasing rank, which was not related to coal type. It is suggested that the observed trend is related to a decrease in the heterogeneity of the pore surfaces, and subsequent increased coverage by the adsorbate, as coal rank increases. Desorption rate studies on crushed samples show that dull coals desorb more rapidly than bright coals and that desorption rate is also a function of rank. Coals of lower rank have higher effective diffusivities. Mineral matter was found to have no influence on desorption rate of these finely crushed samples. The evolution of the coal pore structure with changing rank is implicated in diffusion rate differences.