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.     

Chemometric analysis of functional groups in fossil remains of the Dicroidium flora (Cacheuta, Mendoza, Argentina): Implications for kerogen formation

Studied samples include eight Gondwanan species of the Dicroidium flora: seed ferns (3), conifer (1), cycad-related (1), unknown affinity gymnosperms (2), and one undetermined axis from two Middle to Upper Triassic localities (Cacheuta, Mendoza, central western Argentina). Based on differing preservation states and sample treatments, four sample forms are established: (1) compressions, (2) cuticles, (3) cuticle-free coalified layers, and (4) associated coal samples. The purpose of the study is firstly to analyze the sample forms using Fourier transform infrared (FTIR) spectrometry, contributing to filling an existing gap of chemical information for Gondwanan pant fossil remains. Secondly, semi-quantitative chemical parameters, calculated by area integration of infrared spectra, are treated using principal component analysis to infer statistical groupings as a function of chemical structures (functional groups). From the initial two-component solution, based on the 8 × 41 data matrix, a subset matrix (4 × 29) could be isolated which also yielded a two-component solution (in each case, cumulative explained variance is at least 89%). Results include the distinction between the coaly forms (1) compressions and (3) cuticle-free coalified layers mainly based on the carbonyl contents and branching and length of the hydrocarbon side chains. The highly aliphatic nature of cuticles, which is indicative of biomacromolecules (cutin), is noted. Similarities in functional groups are recorded with types of kerogen and coal macerals. The result enables us to postulate that the functional groups characterizing the different modes of preservation of our fossil remains are likely related to the propensity to generate oil and gas/condensate from the kerogen. Our data have the potential for future studies with implications for chemotaxonomy, molecular taphonomy, and paleoclimatology.     

Structural modifications of vitrinite and alginite concentrates during pyrolitic maturation at different heating rates. A combined infrared, C NMR and microscopical study

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

FTIR-derived characteristics of fossil-gymnosperm leaf remains of Cordaites principalis and Cordaites borassifolius (Pennsylvanian, Maritimes Canada and Czech Republic)

Cordaites principalis and Cordaites borassifolius, gymnosperm trees of the Carboniferous, are distinguished based on compression and cuticular morphology. A new distinction between them is suggested on the basis of differences in functional groups. Cuticular and compression spectra of C. borassifolius have lower CH₂/CH₃ ratios, suggesting more branched aliphatic chains in comparison with cuticles and compressions of C. principalis. Other differences are observed with Fourier transform infrared spectroscopy (FTIR) technique, but they vary from sample to sample of the two species to suggest other than chemotaxonomic-based sources of variations.     

Early coalification features as approached by solid state C CP/MAS NMR spectroscopy

Solid state ¹³C CP/MAS NMR spectroscopy and ultimate analysis have been applied to a study of samples from the Pleistocene Drama lignite and its successive modern analogue, the Philippi peat, in northeastern Greece. The succession from peat to lignite resulted in a C enrichment averaging 10.7% and depletion in H and O averaging 6.5 and 18.5%, respectively. Early coalification resulted in the degradation of methoxyl groups, carbohydrates and carboxylic groups, whereas the aliphatic carbons were less affected. However, organic geochemical alteration seems to depend strongly on the initial peatification conditions. The “aromaticity” decreases from the stage of peat to lignite, as a result of the significant degradation of lignin precursors.     

Analysis of modern and fossil plant cuticles by Curie point Py-GC and Curie point Py-GC-MS: Recognition of a new, highly aliphatic and resistant biopolymer

This paper investigates to what extent the chemical constituents of plant cuticles (waxes and cutin) can survive diagenesis. Recent and fossil plant cuticles were analyzed by means of Curie point pyrolysis-gas chromatography and Curie point pyrolysis-gas chromatography-mass spectrometry. Recent cuticles were analyzed without treatment, after solvent extraction and after cutin depolymerization. Extensive series of straight-chain alkanes, alk-1-enes and α,ω)-alkadienes dominate the pyrolysates, especially after removal of the wax and cutin. ¹³C-NMR spectroscopy of the residue after removal of the cutin confirmed the presence of a new, highly aliphatic biopolymer and a polysaccharide fraction.The abundance of straight-chain alkanes, alk-1-enes and α,ω-alkadienes in the fossil plant cuticles indicates the chemical resistence of the biopolymer to diagenesis and may explain the occurrence of straight-chain aliphatic moieties in organic-matter-rich sediments and coals as revealed by “C-NMR spectroscopy and flash pyrolysis methods. The highly aliphatic biopolymer may function as an important oil precursor.     

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.     

Solid bitumen reflectance and Rock-Eval Tmax as maturation indices: an example from the “Nordegg Member”, Western Canada Sedimentary Basin

Marine, organic-rich rock units commonly contain little for vitrinite reflectance (VR₀) measurement, the most commoly used method of assessing thermal maturity. This is true of the Lower Jurassic “Nordegg Member”, a type I/II, sulphur-rich source rock from the Western Canada Sedimentary Basin. This study examines the advantages and pitfalls associated with the use of Rock-Eval T_max and solid bitumen reflectance (BR₀) to determined maturity in the “Nordegg”. Vitrinite reflectance data from Cretaceous coals and known coalification gradients in the study area are used to extrapolate VR₀ values for the “Nordegg”.T_max increases non-linearly with respect to both BR₀ and extrapolated VR₀ values. A sharp increase in the reflectaance of both solid bitumen and vitrinite occurs between T_max 440–450°C, and is coincident with a pronounced decrease in Hydrogen Index values and the loss of solid bitumen and telalginite fluorescence over the same narrow T_max interval. This T_max range is interpreted as the main zone of hydrocarbon generation in the “Nordegg”, and corresponds to extrapolated VR₀ values of 0.55–0.85%. The moderate to high sulphur contents in the kerogen played a significant role in determining the boundaries of the “Nordegg” oil window.A linear relationship between BR₀ and extrapolated VR₀, as proposed elsewhere, is not true for the “Nordegg”. BR₀ increases with respect to extrapolated VR₀ according to Jacob's (1985) formula (VR₀=0.618×(BR₀)+0.40) up to VR₀≈0.72% (BR₀≈0.52%). Beyond this point, BR₀ increases sharply relative to extrapolated VR₀, according to the relatioship VR₀ = 0.277 × (BR₀) + 0.57 (R² = 0.91). The break in the BR₀−VR₀ curve at 0.72%VR₀ is thought to signifiy the peak of hydrocarbon generation and represents a previously unrecognized coalification jump in the solid bitumen analogous to the first coalification jump of liptinites.     

Organic geochemistry of Amynteo lignite deposit,northern Greece: a Multi-analytical approach

Several lignite samples were collected from boreholes of the Amynteo opencast lignite mine, northern Greece. Organic geochemical characteristics were investigated with the help of various analytical techniques, comprising Gas Chromatography (GC) and Gas-chromatography-Mass Spectrometry (GC-MS), Fourier Transform Infrared Spectroscopy (FTIR), solid-state Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopy, petrographical measurements as well as determination of bulk parameters. In the low rank (Rr = 0.21%) Amynteo lignites, huminite is the most abundant maceral group, inertinite has relatively low percentages and liptinite concentrations are rather high. Carbon Preference Index (CPI) reveals the predominance of odd-numbered, long-chained aliphatic hydro-carbons, which is related to a higher terrestrial plant input. The Pr/Ph ratio suggests that reducing conditions were persistent during peatification. Gymnosperm biomarkers such as isoprimarane, abietane, phyllocladane and sandaracopimarane, as well as angiosperm indicators (lupane) and hopanoid compounds with bacterial origin were identified. Analyses of the aromatic fractions revealed the presence of naphthalene, alkyl benzenes and phenols, pyrene, cadalene, cadinane, fluoranthene and dibenzofurane. Based on the FTIR analysis, aliphatic and oxygen containing structures were prevailed over the aromatic moieties. The intensity of the mineral bands was preferentially increased in the FTIR spectra of insoluble material. According to NMR analysis, the aliphatic carbons (0–50 ppm) have higher proportions comparing to aromatic carbons (100–160 ppm). The aromaticity fraction is low (fa = 0.32), as expected for these low rank coals. The presence of free organic radicals and Fe³⁺ and Mn²⁺ paramagnetic ions was revealed by EPR. In summary, the combined application of complementary analytical techniques allowed a deep inside into the geochemical characteristics of Amynteo lignites.     

实验变形煤的光性组构分析

三种R_max^o分别为0.67%,3.41%和4.90%的煤样,在t=350-700℃、P_c=400-600MPa、ε=10%-30%、ε=3.63×10^-4-2.59×10^-5s^-1条件下的变形实验表明:(1)煤光性组构的成因是芳环层片在构造应力作用下重新定向所致,重新定向的主要机制是煤化过程中芳环层片的择优成核生长,同时存在物理转动定向机制的作用;(2)芳环层片的重新定向主要发生在煤级相对较低阶段,VRI的Z轴主要反映这一阶段的构造应力方向;(3)YRI的形态特征并非仅与有限应变有关,它不能直接作为有限应变分析的标志。     

Functional groups in a single pteridosperm species: Variability and circumscription (Pennsylvanian, Nova Scotia, Canada)

Multiple foliar specimens of the Late Pennsylvanian fossil pteridosperm [gymnosperm] Alethopteris zeilleri (Ragot) Wagner were collected from one restricted stratigraphical horizon in the Canadian Sydney Coalfield. Variability of functional-group distribution using FTIR technique was studied in compressions, adaxial versus abaxial cuticles, and in unseparated cuticles as a function of maceration time from 48 to 168 h. The results obtained document spectral variability that could be expected within specimens of one species. For example, CH₂/CH₃ and Al/ox ratios can differ by as much as 20% of the values. Moreover, the experiments performed confirm that by using a previously established maceration protocol, long maceration periods do not bias FTIR spectra in terms of oxygenation overprinting. The inference that this cuticle is robust, under the given diagenetic level, probably reflects a reassuring degree of chemical fidelity of the Pennsylvanian plant to support Carboniferous chemotaxonomic observations.     

Properties, origin and nomenclature of rodlets of the inertinite maceral group in coals of the central Appalachian basin, U.S.A.

Resin rodlets, sclerenchyma strands and woody splinters, which are collectively called rodlets, were studied by chemical, optical petrographic, and scanning-electron microscopic (SEM) techniques. A study was made of such rodlets from the bituminous coal beds of the central Appalachian basin (Pennsylvanian; Upper Carboniferous) of the United States. Comparisons were made with rodlets from coal beds of the Illinois basin, the Southern Anthracite Field of Pennsylvania, the St. Rose coal field of Nova Scotia, and European and other coal fields. In order to determine their physical and chemical properties, a detailed study was made of the rodlets from the Pomeroy coal bed (high volatile A bituminous coal; Monongahela Formation; Upper Pennsylvanian) of Kanawha County, West Virginia. The origin of the rodlets was determined by a comparative analysis of a medullosan (seed fern) stem from the Herrin (No. 6) coal bed (high volatile C bituminous coal; Carbondale Formation) from Washington County, Illinois. Rodlets are commonly concentrated in fusain or carbominerite layers or lenses in bituminous coal beds of the central Appalachian basin. Most of the rodlets examined in our study were probably derived from medullosan seed ferns. The three types of rodlets are distinguished on the basis of cellularity, morphology and fracture.The resin rodlets studied by us are noncellular and appear to be similar in properties and origin to those found in coal beds of the Middle and Upper Pennsylvanian of the Illinois basin. The resin rodlets extracted from the Pomeroy coal bed exhibit high relief and high reflectance when polished and viewed in reflected light; they are opaque in transmitted light. In cross section, the resin rodlets are oval to round and have diameters ranging from 60 to 450 μm. Many are solid, but some have vesicles, canals or cavities, which are commonly filled with clay, probably kaolinite. Typically, they have distinct fracture patterns (“kerfs”) in longitudinal and cross sections and many are characterized by dense (probably oxidized) rims. The orientation and amounts of void space and mineralization of resin rodlets in coal have resulted in much confusion in their recognition and classification. The resin rodlets are petrographically recognized as sclerotinites of the inertinite maceral group. We here propose that resin rodlets be assigned to the maceral variety of sclerotinites termed “resino-sclerotinite” because of their presumable resinous origin. Other investigators have confused some fusinitized resin rodlets with fungal masses, which have different morphological properties and which probably have different chemical properties. We here propose that such fungal masses be assigned to the maceral variety of sclerotinites termed “fungo-sclerotinite.”The sclerenchyma strands examined in our study are cellular, thick-walled, and crescent-shaped in cross section. They exhibit high reflectance and high relief and belong to semifusinite and fusinite of the inertinite maceral group. Sclerenchyma strands are commonly associated with resin canals in Medullosa and related seed-fern genera, which are common in coal balls of the Illinois basin. We here propose adoption of the maceral varietal terms “sclerenchymo-fusinite” and “sclerenchymo-semifusinite” for these bodies.The woody splinters in the Pomeroy coal bed are cellular and thin-walled and have scattered pits as much as a few microns in diameter. They are dark brown to black in transmitted light and commonly have a lower reflectance than the resino-sclerotinite and sclerenchymo-fusinite of the Pomeroy coal. The woody splinters belong to semifusinite and fusinite of the inertinite maceral group. The maceral varietal terms “xylemo-semifusinite” and “xylemo-fusinite” are here proposed for these bodies.Elemental chemical data for the resin rodlets of the Pomeroy coal bed of the central Appalachian basin indicate that resin rodlets have significantly lower atomic H/C and O/C ratios than do sclerenchyma strands and woody splinters. The lower atomic H/C and O/C ratios of the resin rodlets correlate with the highest reflectance. In the coal ball medullosan seed-fern stem from the Herrin (No. 6) coal bed of the Illinois basin, the reflectances of the resin rodlets, woody splinters and sclerenchyma strands are similar and comparable to those of associated vitrinite in the coal ball stem and in the attached coal. However, resin rodlets and sclerenchyma strands in the attached coal have significantly higher reflectances, similar to those of the Pomeroy coal.     

Nuclear magnetic resonance studies of ancient buried wood—II. Observations on the origin of coal from lignite to bituminous coal

Coalified logs ranging in age from Late Pennsylvania to Miocene and in rank from lignite B to bituminous coal were analyzed by ¹³C nuclear magnetic resonance (NMR) utilizing the cross-polarization, magic-angle spinning technique, as well as by infrared spectroscopy. The results of this study indicate that at least three major stages of coalification can be observed as wood gradually undergoes transformation to bituminous coal. The first stage involves hydrolysis and loss of cellulose from wood with retention and differential concentration of the resistant lignin. The second stage involves conversion of the lignin residues directly to coalified wood of lignitic rank, during which the oxygen content of intermediate diagenetic products remains constant as the hydrogen content and the carbon content increases. These changes are thought to involve loss of methoxyl groups, water, and C₃ side chains from the lignin. In the third major stage of coalification, the coalified wood increases in rank to subbituminous and bituminous coal; during this stage the oxygen content decreases, hydrogen remains constant, and the carbon content increases. These changes are thought to result from loss of soluble humic acids that are rich in oxygen and that are mobilized during compaction and dewatering. Relatively resistant resinous substances are differentially concentrated in the coal during this stage. The hypothesis that humic acids are formed as mobile by-products of the coalification of lignin and function only as vehicles for removal of oxygen represents a dramatic departure from commonly accepted views that they are relatively low-molecular-weight intermediates formed during the degradation of lignin that then condense to form high-molecular-weight coal structures.     

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.     

Chemometric study of functional groups in different layers of Trigonocarpus grandis ovules (Pennsylvanian seed fern, Canada)

We examined four dispersed, coalified ovules, Trigonocarpus grandis, of medullosalean seed-fern affinity from the Late Pennsylvanian age Sydney Coalfield, Canada, which represent the larger type of the 7–8 cm trigonocarpalean form species. At first glance it appears that the ovules are preserved like the usual Carboniferous foliar compressions, i.e. one coalified layer with one preserved anatomical tissue, the cuticle. However, careful sample preparation uncovered at least three coalified layers, and Schulze’s oxidative maceration process, which dissolves the coalified material, revealed several tissue layers. Altogether, eight sample forms were defined: (i) coalified layer, (ii) cuticle A, (iii) cupric + vitrain, (iv) vitrain, (v) cupric, (vi) cuticle B, (vii) alkaline solution and (viii) added coal seam material. The purpose of the study was twofold: first, to systematically analyze the forms by way of Fourier transform infrared (FTIR) spectrometry to fill a gap in chemical information that exits for coalified trigonocarpalean ovules of Carboniferous seed ferns; second, to use principal component analysis to focus on groupings as a function of chemical structure (functional groups) and to assess the different fossil forms in terms of FTIR chemical parameters, based on a 8 × 49 data matrix.Results include distinction among the three coaly sample forms, coalified layer (i), cupric + vitrain (iii) and cupric (v), based mainly, but not exclusively, on differences in carbonyl content, as well as length and branching of the polymethylenic chains. Important to note is the high aliphatic content of the cuticles as a signature of the biomacromolecules cutan/cutin. In particular, new insights into the structure of the original ovule are presented, and differences in chemistry are mainly a result of the complex structure of the precursor plant organ.     

Geological and laboratory evidence for early generation of large amounts of liquid hydrocarbons from suberinite and subereous components

Suberinite, and subereous components of amorphous nature, comprise largely unrecognized, proficient sources of liquid hydrocarbons. Due to difficulties in recognizing the presence of subereous components and suberinite in organic sediments, the contributions of these liptinitic components to the organic input of source rocks are easily underestimated. Severe chemical alterations of suberinite in the vitrinite reflectance range of R_o = 0.35–0.60% are demonstrated. Organic geochemical data, obtained from samples subjected to natural maturation, reveal that subereous components/suberinite undergoes early thermal degradation to generate large amounts of hydrocarbons below R_o = 0.60%. Data obtained from laboratory maturation of immature, suberinite-rich coals indicate that about 50% of the potential of suberinite for generating C₁₂₊ hydrocarbons has already been exhausted during natural maturation of the samples, prior to the onset of the traditionally defined “oil window”. The present data (a) contradict the assumption that suberinite is mainly sourced by selective preservation/enrichment of a stable, highly aliphatic biopolymer, i.e. “suberan” and (b) suggest that suberinite contains appreciable amounts of aliphatic and aromatic moieties which are released at low thermal stress.     

Influence of maceral content on δ13C and δ15N in a Middle Pennsylvanian coal

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

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

Burial history and thermal evolution of Westphalian coal-bearing strata in the Campine Basin (NE Belgium)

A 1D-modelling program has been applied to reconstruct the burial and thermal histories of two exploration boreholes, KB172 and KB174, located in the Campine Basin. The results show differences in geological histories. The coalification of the Westphalian A and B strata in KB174 (0.66–0.98% R_o) was pre-Permian. Calculated maximum temperatures, based on borehole data and vitrinite reflectance, regional thicknesses and a heat flow of 84 mW/m² during the Late Westphalian, range from 110 °C at the top to 175 °C at the bottom of the Westphalian cored in this borehole. The high coalification (0.85–1.30% R_o) of the Westphalian C and D strata in KB172 could be the result of the deposition of 2500 m of Upper Permian to Middle Jurassic sediments in combination with elevated heat flows (71–80 mW/m²). Two coalification periods, i.e. Late Westphalian and Middle Jurassic, are suggested for this borehole. The simulated maximum temperatures range from 130 °C at the top to 175 °C at the bottom of the investigated Westphalian C and D. The differences in the burial and thermal histories of both boreholes can be related to the activity of the transversal Donderslag Fault, a major structural element in the Campine coalfield, and the Roer Valley Graben.     

Study of petroleum generation by pyrolysis—I. Pyrolysis experiments by Rock-Eval and assumption of molecular structural change of kerogen using13C-NMR

Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%R_o) measurement, maceral observation, infrared spectroscopy (IR) and¹³C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when R_o does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by¹³C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.