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.     

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.     

Size and maceral association of pyrite in Illinois coals and their float-sink fractions

The amount of pyrite (FeS₂) removed by physical cleaning varies with differences in the amount of pyrite enclosed within minerals and of free pyrite in feed coals. A microscopic procedure for characterizing the size and maceral association of pyrite grains was developed and evaluate by testing three coals and their washed products. The results yield an index to the cleanability of pyrite. The index is dependent upon particle size and has intermediate values for feed coals, lower values for cleaned fractions, and higher values for refuse fractions; furthermore, it correlates with pyritic sulfur content. In the coals examined, the summed percentage of grain diameters of pyrite enclosed in vitrinite, liptinite, and bi- and trimacerite provides a quantitative measure of the proportion of early diagenetic deposition of pyrite.     

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.     

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.     

Elemental concentrations and their distribution in two bituminous coals of different paleoenvironments

The vertical distributions of major and minor elements in two high-volatile bituminous coals of Eastern Tennessee are compared. The coals studied are the Pewee, deposited in a fresh-water environment, and the Upper Grassy Spring, previously thought to be influenced by a late incursion of marine water.X-ray fluorescence analyses were performed on a continuous series of specimens obtained from full-face channel samples representing the entire thickness of each seam. Correlation coefficients (r) for all element pairs show high positive correlations for element pairs normally associated with clay minerals. Equally good correlations were observed for (Si, Ti) and (Al, Ti), suggesting that titanium is associated with clay minerals in both coals. Strontium and phosphorous showed a high positive r factor for both the Upper Grassy Spring and the Pewee.Major differences were found to exist in the concentrations and distributions of sulfur, iron, and arsenic in the Upper Grassy Spring and Pewee seams. The Upper Grassy Spring contains an order of magnitude more sulfur than the Pewee as well as several times as much iron and arsenic. The element concentrations and especially their distributions in the Upper Grassy Spring suggest an earlier time for the marine incursion than previously reported. In fact, there is evidence that this coal deposit may have been influenced by marine conditions from its inception.     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Adsorption characteristics of natural organic matter on activated carbons with different pore size distribution

The adsorption characteristics of natural organic matter (NOM) were investigated on the basis of fluorescence excitation emission matrix (EEM) by using four different coal-based activated carbons (ACs). For each AC, batch adsorption isotherms were analyzed using a modified Freundlich isotherm model on the basis of the fluorescence intensity of three major fluorescence peaks appeared in the fluorescence EEM reported to be reflective of the humic acid-like (P1), fulvic acid-like (P2) and aromatic protein-like (P3) substances, respectively, together with the well-used overall quality indices of dissolved organic carbon (DOC) and ultraviolet absorbance at the wavelength of 260 nm (UV260). It was found that, for all five quality indices, the adsorption capacity differed with the ACs used, and the modified Freundlich isotherm constant K estimated for P1, P2 and P3 was in close correlation with that of the total organic matter evaluated by DOC. Moreover, no matter which AC was concerned, the magnitude of the estimated K and the removal rate over a broader range of AC dose for P3 were apparently smaller than those for P1 and P2, suggesting the adsorbability of aromatic protein-like substances was lower than that of the humic acid-like and fulvic acid-like substances. The dependency of the adsorption capacity of NOM on the volume of pores in some specific size ranges of the ACs was also revealed.     

Amino acid and amino sugar yields and compositions as indicators of dissolved organic matter diagenesis

Microbial decomposition experiments were used to characterize changes in the amino acid and amino sugar yields and compositions of natural marine substrates during early diagenesis in seawater. On average, 63% of added carbon and 68% of added nitrogen were removed within the first 30 days of decomposition. In all cases, amino acid utilization accounted for a substantial fraction of the removed C and N. Carbon-normalized amino acid yields decreased to less than 50% of their starting values and most of this change occurred within the first 10 days of decomposition. Increases in the concentrations of amino sugars and decreases in the GlcN:GalN ratio in particulate organic matter (POM) illustrated the significance of microbial production during the decomposition of added substrates. Changes in the mol % composition of amino acids during early diagenesis were substantial but highly variable with substrate. Previous survey data collected from the same region were used in conjunction with the experimental data to investigate the utility of several established amino acid-based indices of organic matter diagenesis. This comparison showed that a combination of these degradation indexes is most effective for describing the diagenetic state of dissolved organic matter (DOM). Carbon-normalized amino acid yields were found to be the most effective indicator for early diagenesis. Relative abundances of amino acids were effective indicators of intermediate stages of diagenesis and the mol % composition of the non-protein amino acid γ-Aba (γ-aminobutyric acid) was an effective indicator of advanced DOM diagenesis.     

倍半萜类分布和组成与低熟烃源岩有机质热演化研究

通过对低成熟烃源岩中8α(H)-升补身烷和8β(H)-升补身烷以及2-乙基甲基四氢化萘和1-乙基甲基四氢化萘分布和组成特征的剖析,研究了8α(H)-升补身烷/8β(H)-升补身烷比值和1-乙基甲基四氢化萘/2-乙基甲基四氢化萘比值与镜质组反射率R°之间的关系,发现在R°＜0.60%时,这两个比值变化幅度很大,表明这两个比值在低成熟阶段是衡量有机质热演化程度的有效指标.     

Hydrocarbon products of coals as revealed by pyrolysis-gas chromatography

The hydrocarbon products generated and released from coals continue to be debated. The Mesozoic and Cenozoic southern hemisphere coals have been described as being capable of generating significant quantities of heavy hydrocarbons (oil-like material) when compared to the Paleozoic coals of the northern hemisphere because of changes in the coal forming community. This hypothesis was examined by comparing the pyrolysis-gas chromatography results of a collection of coals. Preliminary results indicate that the most significant difference in pyrolytic products is in the less than nC₁₅ fraction. The data further indicate that coals generate similar types of hydrocarbons independent of age or geographic position if they contain similar bulk maceral content. Coals rich in vitrinite generate predominately aromatic hydrocarbons with lesser amounts of n-paraffins. Coals rich in algae and other exinites generate largely paraffinic hydrocarbons. Coals rich in resins generate naphthenic and aromatic hydrocarbons. The petroleum generating potential of coals also depends on the coal's expulsion efficiency, which is not addressed by this study.     

Characterisation of dispersed organic matter from lower Palaeozoic metasedimentary rocks by organic petrography, X-ray diffraction and micro-Raman spectroscopy analyses

Dispersed organic matter (DOM) concentrates of C-rich rocks from areas with different metamorphic characteristics were studied by organic petrography, X-ray diffraction (XRD) and micro-Raman spectroscopy analysis. The concentrates contain several types of DOM with different morphologies, reflectance, X-ray diffraction and micro-Raman characteristics.Four different morphological types were identified in the two studied areas. The different types have different distributions and their reflectance is quite variable in the four types, with a dominance of the highest reflectance values in the DOM from the area with the highest metamorphic grade.XRD analyses of samples from the areas reveal the presence of fine graphite together with non-graphitised carbons.The Raman spectral profiles show the usual bands G (1582 cm⁻¹) and D1 (1350 cm⁻¹), on the first-order Raman spectrum, and S1 (2700 cm⁻¹) on the second-order spectrum. Additional weaker bands, D2 (1620 cm⁻¹), and more rarely D3 (1500 cm⁻¹) and S2 (2900 cm⁻¹), are present. These are characteristic for disordered carbons in the different types of DOM and in both studied areas. However, the Raman parameters (D1/G intensity area ratio and the frequency and width of G band) indicate variable degrees of organisation in all DOM types.The existence of different types of DOM with different degrees of ordering in the same lithologies and metamorphic grade seems to be related to different organic precursors, as they are graphitised to different extents under the same metamorphic conditions. However, in the same lithologies and metamorphic grade, the existence of various stages of graphitisation within the same type of DOM can only be explained though the interaction of DOM with the metamorphic fluids present in the rocks. The ordering graphitisation process may be due to the existence of metamorphic fluid circulation events with a variety of compositions.     

Mineral matter in coals and their reactions during coking

Degradation of coke in the blast furnace is influenced by its inherent mineral matter, the formation of which is itself dependent upon the nature of the coal mineral matter. To date few studies have been made of coke mineralogy and its relationship to the mineralogy of the parent coal. In this study the effect of carbonisation on coal mineral matter has been investigated by a detailed quantitative mineralogical examination of nine cokes and their parent coals. The quantitative analysis was performed on X-ray diffraction patterns of the mineral matter of cokes and coals, using SIROQUANT^™. Coke mineralogy and its composition varied strongly between cokes, more strongly than variations in elemental composition of the ash. The mineral matter in the studied cokes consisted of crystalline mineral phases and also significant levels of amorphous phase (ranging between 44 and 75%). Decomposition of clays such as kaolinite, montmorillonite, illite and chamosite produced the amorphous phase and some of the crystalline mineral phases such as mullite, γ-alumina, spinel, cristobalite and leucite. The type of association of mineral matter in coals had an important role in how the clays decomposed. For example, association of kaolinite with silica-bearing minerals in intimate intermixture favoured formation of mullite over γ-alumina. Akermanite and diopside result from reaction of kaolinite with associated calcium bearing minerals (calcite, dolomite or ankerite). Quartz, fluorapatite and the three polymorphs of TiO₂ (anatase, brookite and rutile) were the coal minerals that were least affected during carbonisation, as they were also found in the cokes, yet even they were affected in some cases.     

Evaluating the gas content of coals and isolated maceral concentrates from the Paleocene Guasare Coalfield,Venezuela

This work presents the results from evaluating the gases sorbed by coal samples extracted from the Paleocene Guasare Coalfield (Marcelina Formation, northwestern Venezuela), as well as by their distinct maceral concentrates. The aim of this work has been to obtain an initial experimental main value of the gas content per unit weight of high volatile bituminous A coal samples from the open-pit Paso Diablo mine. An additional goal was to study differences in the CH₄ storage ability of the distinct maceral groups forming part of the coal matrix. Both the coal samples and the maceral concentrates were studied by thermogravimetric analysis (TGA) in order to determine the temperature to be used in subsequent experiments. On-line analyses of hydrocarbons (C₁, C₂, C₃) and CO₂ yielded gas concentrations, plus δ¹³C values. Thermogenic gas is prevalent in the Guasare coals with vitrinite reflectance (%R_o) values from 0.65% to 0.88%. The amount of gas retained in the coals and maceral concentrates was measured with a special device that allows determination of the volume of gas sorbed by a solid sample subjected to controlled thermal treatment. The average coalbed gas concentration obtained was 0.51 cm³/g. The following list of maceral concentrates shows the relative capacity for the volume of sorbed gas per unit weight: inertinite > low-density vitrinite > liptinite ≈ high-density vitrinite. It is concluded that the gas volumes retained in the distinct maceral concentrates are not controlled by porosity but rather by their microscopic morphology.     

The origin and evolution of chondrites recorded in the elemental and isotopic compositions of their macromolecular organic matter

Extraterrestrial organic matter in meteorites potentially retains a unique record of synthesis and chemical/thermal modification by parent body, nebular and even presolar processes. In a survey of the elemental and isotopic compositions of insoluble organic matter (IOM) from 75 carbonaceous, ordinary and enstatite chondrites, we find dramatic variations within and between chondrite classes. There is no evidence that these variations correlate with the time and/or location of chondrite formation, or with any primary petrologic or bulk compositional features that are associated with nebular processes (e.g., chondrule and volatile trace element abundances). Nor is there evidence for the formation of the IOM by Fischer-Tropsch-Type synthesis in the nebula or in the parent bodies. The elemental variations are consistent with thermal maturation and/or oxidation of a common precursor. For reasons that are unclear, there are large variations in isotopic composition within and between chondrite classes that do not correlate in a simple way with elemental composition or petrologic type. Nevertheless, because of the pattern of elemental variations with petrologic type and the lack of any correlation with the primary features of the chondrite classes, at present the most likely explanation is that all IOM compositional variations are the result of parent body processing of a common precursor. If correct, the range of isotopic compositions within and between chondrite classes implies that the IOM is composed of several isotopically distinct components whose relative stability varied with parent body conditions. The most primitive IOM is found in the CR chondrites and Bells (CM2). Isotopically, the IOM from these meteorites resembles the IOM in interplanetary dust particles. Chemically, their IOM resembles the CHON particles of comet Halley. Despite the large isotopic anomalies in the IOM from these meteorites, it is uncertain whether the IOM formed in the interstellar medium or the outer Solar System, although the former is preferred here.     

Mercury-binding forms in coals and their geological provenances in coals of different types

Mercury (Hg) is an element of environmental and geological significance. Quantification of different Hg-binding forms is crucial to understand geological Hg provenances and associated geochemical processes during coal formation. In this study, seven coal samples were selected, according to coal rank (i.e., middle volatile bituminous, C-3; low volatile bituminous, C-2; anthracite, C-1), chemical anomalies (high S coal, IBC-105; high Cl coal, C22650) and sampling environment (fresh coal, LH; weathered coal LHW), to determine their Hg-binding forms using well-established sequential extraction procedures coupled with sink–float experiment. In the thermally metamorphosed samples C-1 and C-2, a comparative enrichment of total Hg relative to C-3 is observed. Silicate- and organic-bound Hg are the dominant Hg-binding forms in C-1, suggesting possible Hg sources from magma silicate and secondary Hg enrichment by adsorption. Sulfide- and organic-bound Hg are the most abundant Hg-binding forms in IBC-105, whereas only organic-bound Hg dominates in CC22650. Weathering processes are suggested to transform the abundant sulfide-bound Hg in LH to silicate- and organic-bound Hg in its weathering product LHW.     

Mineral matter in coals: cleat minerals and their origin in some coals from the english midlands

In four coal seam profiles from the Cannock Coalfield, West Midlands, the cleat (joint) frequency is a function of lithotype (greatest in vitarin) and is inversely related to bed thickness. The cleat minerals were studied: (1) under the microscope (optical and electron); (2) by X-ray diffraction; and (3) chemically. The minerals present are pyrite, marcasite, sphalerite, galena (sulphides), quartz, kaolinite (silicates), ankerite, calcite (carbonates) and apatite. This sequence has features in common with diagenetic sequences recorded in other rock types and it is concluded that the cleat minerals in coal form in response to pore fluid evolution and movement during burial diagenesis. The elements are thought to originate from both the coal and the associated sediments, mainly mudrocks. Similarities in diagenetic sequences are in part a reflection of the importance of organic maturation reactions in all the rock types in the sequence, whereas differences are attributed to the dominance of these reactions in the coal itself.     

北淮阳地区不同变形-变质煤的元素分布及其影响因素

通过对大别造山带前陆北淮阳地区石炭纪高煤级煤的X射线荧光光谱分析,探讨了不同变形-变质类型煤中常量元素的分布规律及其影响因素。结果表明:构造-热作用具有使Al³⁺、K⁺、Si⁴⁺、Ti⁴⁺在煤体中富集,P⁵⁺、Fe²⁺+Fe³⁺、Mn²⁺Na⁺、Ca²⁺、Mg²⁺向煤体外迁移的趋势;在弱应力带富集Al³⁺、K⁺、Ti⁴⁺、Na⁺、Ca²⁺;在强应力带富集Si⁴⁺、P⁵⁺、Fe²⁺+Fe³⁺、Mg²⁺。岩浆热变质类型煤和构造-热变质类型煤的w(SiO₂)/w(Al₂O₃)和w(K₂O)/w(Na₂O)值显著增大,与岩浆岩中SiO₂及K₂O质量分数偏高有重要的成因联系。