首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
The functional groups of brown coal lithotypes, their humic acids and kerogens were investigated by elemental analysis and quantitative infrared spectroscopy using absorption coefficients.An inverse relationship is reported between the concentrations of kerogen and humic acids for each lithotype and significant variation in the levels of humic acids with lithotype are attributed to changing higher plant input and depositional environments.The structural implications of observed trends in absorption coefficients and their usefulness as a rapid method of functional group analysis has been investigated. Using this infrared technique, kerogen structures as reflected in functional group analyses were found to exhibit a dependance on lithotype, although no significant variation in the functionality of the humic acid structures was observed.  相似文献   

2.
A quantitative 13C-NMR technique was applied to humic acids, isolated from total solvent extracts obtained from coals, varying in rank from lignite to medium volatile bituminous. The results from elemental analysis and 13C-NMR structural ratios are interpreted in the form of three distinct structural phases in the maturation of coal humic acids. These phases reflect the rank of the parent coals. A decrease in polar functional group content and corresponding increase in aromaticity is observed with increasing maturation of humic acid chemical structure. Limits are postulated for the oxygen content and level of aromaticity for humic acids derived from higher rank coals.  相似文献   

3.
Victorian brown coal occurs in five major lithotypes distinguishable by colour index, petrography and bulk chemical analyses. The distributions of solvent extractable (free) and base hydrolysable (bound) n-alkanes, n-monocar?ylic acids, n-?,ω-dicar?ylic acids, n-ω-hydroxycar?ylic acids and n-alcohols were determined for samples of each of the five lithotypes (lithotype profile) and for seven samples of identical lithotype classification spanning a 100 m interval (depth profile) taken from a continuous bore core. The distributions of free molecular components in all classes are indicative of the predominant higher plant origin of this immature coal and provide strong support for the view that different lithotypes have derived from different, yet fairly specific paleobotanical communities. Despite an overall similarity in the distributions of aliphatic components from samples of identical lithotype classification, changes in the absolute concentrations and carbon preference indices (CPIs) of specific functional classes are observed in response to catagenetic influences even across the very small rank interval of the depth profile samples. Molecular distributions of bound components are similar to those of their free counterparts except that CPIs are generally lower and the relative contributions of lower molecular weight homologues (i.e. <C22) are higher. Thedistributions of bound dicar?ylic acids and hydroxycar?ylic acids appear to reflect variations in the oxic/anoxic nature of the depositional paleoenvironments.  相似文献   

4.
The River Gem coal bed (upper Westphalian A) was sampled at five sites in a single mine in Whitley County, Kentucky. Previous petrographic and sulfur analyses of the collected interval samples showed that the coal bed could be divided into a basal low-sulfur lithotype, a middle high-sulfur bone lithotype and an upper high-sulfur lithotype. At one location a high-sulfur rider unit is present. In this study we have conducted detailed palynological analyses on all of the interval samples and ash geochemistry on the upper high-sulfur lithotype intervals and two of the basal high-sulfur basal lithotype intervals.Geochemical analyses show that As and Pb are generally high in the high-sulfur upper lithotypes from all five sites. Carbonates, having associated high levels of Ba and Sr, are important in the ash geochemistry of the lower, low-sulfur lithotypes. Ga, Ge and W are enriched in the higher vitrinite lithotypes among the low-sulfur samples. The basal lithotype at each of two sites, which was analyzed in detail, is enriched in yttrium plus the lighter rare earth elements.The basal low-sulfur lithotypes are dominated by arboreous lycopod spores. The middle, low-sulfur portion of the bed is dominated by herbaceous lycopsids (Densosporites) at the base of the unit and becomes increasingly enriched in Lycospora towards the top of the unit indicating that the peat-forming environment became wetter. The greatest arboreous lycopod spore abundances in the upper, high-sulfur portion the bed, along with an overlying marine roof, indicates that peat deposition was terminated by a marine inundation.  相似文献   

5.
Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of HCversus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.  相似文献   

6.
Although petrographic analysis of the lithotypes present in coal samples has been successfully used in the correlation of coal seams, the study of the environments of coal seam deposition, and the evaluation of the mining and cleaning properties of numerous coal seams, coal lithotype analysis is not routinely performed in North America at this time because it is very time consuming and requires the services of a highly skilled petrographer. The objective of this study was to evaluate the capability of one of the newly improved image analysis microscope systems to characterize coal lithotypes and perform automated lithotype analyses on polished block samples of coal.The results of this study show that each of the lithotypes examined, vitrain, clarain, fusain, and durain, yield a characteristic reflectance histogram and that analysis of reflectance histograms taken from a transverse, perpendicular to bedding, down a polished block sample yield results on the kinds and thicknesses of the lithotypes present that are in good agreement with the results obtained by manual methods.  相似文献   

7.
Palaeobotanical studies of the brown coal deposits of the Latrobe Valley have contributed significantly towards an understanding of the age of the deposits, existing climatic conditions and detailed depositional environments. This paper re-assesses some past reconstructions for the Early to Mid Miocene coals using recent information on plant distributions and their bioclimatic significance and on a marine incursion model for coal lithotype formation.The brown coal flora is composed overwhelmingly of rainforest taxa that presently cover a range of different environments within the Australasian region. The application of a bioclimatic prediction model to these taxa allows the construction of consistent and quantitative estimates of climates during coal-forming phases. It is considered that rainfall in the area was more than twice the 850 mm received today, with significant seasonal variation. The mean annual temperature estimate of about 19°C, indicating a mesothermal or subtropical environment, is some 2–5C higher than present and higher than previous estimates. It does, however, correspond with sea-surface temperature estimates for the Southern Ocean at this time.The original model of lithotype formation, which suggests that lithotypes conform to a successional sequence from open water in the lightest coloured lithotypes to raised bog in the darkest lithotypes, is considered to be inconsistent with the evidence for lightening upwards sequences within the coals, a central feature of the proposed marine incursion model of coal formation. The two models are reconciled to some degree by a reinterpretation of the palaeobotanical data and by the postulation of climatic rather than autogenic successional control over lithotype formation.  相似文献   

8.
The methods of sequence analysis have been applied to the onshore Gippsland Basin and in particular to the Latrobe Valley Group coal measures which include up to five coal seams each exceeding 100 m in thickness. The methods appear to provide new depositional concepts to the evolution of these seams, and the development of coal lithotypes. In the eastern half of the Latrobe Valley evidence for marine transgressions into the coal measures are recorded in most of the interseam sediment splits by the presence of contained foraminifera and dinoflagellates. To the west (inland) these splits pinch out into continuous coal. However, they can be followed westwards as enhanced organic sulphur levels along sharply defined boundaries between light coal lithotypes below and dark coal lithotypes above. The dark lithotype immediately overlying each of these boundaries contains the highest sulphur value and warmer climate pollen assemblages (Sluiter et al., 1995, this volume).Colorimeter and lithotype logging strongly supports an upwards lightening cyclicity to coal colour at 12–20 m intervals through the approx. 100 m thick seams, with cycle boundaries defined at sharp planar to undulating surfaces. The lightening upward lithotype cycles together with their unique boundary conditions (i.e. enhanced organic sulphur levels, warm climatic indicators and laterally equivalent marine clay splits) are interpreted as parasequences and parasequence boundaries respectively. Each major coal seam can comprise up to five parasequences and is interpreted to represent deposition during an outbuilding high stand systems tract at one of several maximum periods of Tertiary coastal onlap. The top of each major seam shows evidence of truncation (erosion?) on a regional scale and these surfaces are interpreted to represent the sequence boundaries. The major seams are usually conformably underlain by marine clays and extensive aquifer sands, being deposits of the late transgressive systems tracts. The low stands and early parts of the transgressive systems tracts appear not to be represented in the Latrobe Valley due to its (more) basin margin location, but are probably present down-dip in the equivalent marine facies of the Seaspray Group.Stratigraphic correlation of the sequence boundaries identified in the coal measures to the adjacent, internationally dated marine Seaspray Group, provides a basis for chronostratigraphic correlation of the coal successions to the coastal onlap charts of Haq et al. (Exon Mesozoic-Cenozoic chronostratigraphic chart, version January 1988, and August 1989). From this dating it appears that each major seam is confined to high stands of third order eustatic cycles. It therefore follows that the lithotype cycles (parasequences) that comprise each seam are related to fourth order eustatic cycles. By analogy all the coal cycles may have developed under subtropical conditions as ombrogenous forested peat swamps in a similar manner to the Holocene, though tropical, swamps of Indonesia.  相似文献   

9.
Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption.  相似文献   

10.
13C and 1H NMR spectra were obtained for humic acids isolated from marine sediments. NMR shows great promise in identifying structural components of humic acids as some new and interesting structural features are identified. Aliphatic structures were found to constitute a much larger fraction of humic acids than previously thought, and they appeared to be highly branched. Although the aromatic content of terrestrial humic acid was found to be lower than expected, the aromaticity appears to be a specific discriminator of terrestrial/aquatic source types. A humic acid isolated from an anoxic algal sapropel was found to be composed predominantly of polyuronic acids and different than other aquatic sedimentary humic substances.  相似文献   

11.
Covalent and non-covalent interaction of proteinaceous materials in soils and sediments has been suggested as an important mechanism for immobilizing nitrogen in numerous types of environments. In a previous study (Hsu P.-H., Hatcher, P.G., 2005. New evidence for covalent coupling of peptides to humic acids based on 2D NMR spectroscopy: A means for preservation. Geochimica et Cosmochimica Acta 69, 4521–4533), we provided molecular evidence for covalent, as well as non-covalent, bonding between 15N-labeled peptides and humic acid molecules using the 2D HSQC (heteronuclear single quantum coherence) NMR technique. In this report, we examine the influence of aromaticity and aliphaticity of peptides and humic materials on these covalent and non-covalent interactions. We use 2D NMR techniques to evaluate bonding interactions of 15N labeled peptides, having different aromatic and aliphatic properties, with three humic acids that vary in degree of aromaticity. The peptide containing primarily aromatic amino acid residues is observed to form covalent and non-covalent bonds with mainly aromatic-rich humic acids. The peptide composed of aliphatic amino acid residues shows, on the other hand, only bonding interactions with aliphatic-rich humic acids. These observations provide the first direct molecular evidence that aliphatic functional groups are involved in bonding with proteinaceous materials. The process may play an important role in sequestration of proteinaceous materials in sedimentary systems such as marine systems where the humic materials are mainly aliphatic in nature.  相似文献   

12.
Because of the short supply of high-quality coking coals in certain areas of the world, many methods of improving the coking characteristics of poorly coking or noncoking coals have been examined as alternatives to importing more expensive, better quality coals. Co-carbonization, or the addition of coal-derived or petroleum-derived materials to the coal charge prior to carbonization, has been used on a commercial basis in the Japanese coking industry. These additives have been used in both solid and liquid form as binders in coal briquettes or as direct additions to the coal blend.In this study three different coal lithotypes were sampled from each of three United States bituminous coal seams: (1) a marginally coking high-volatile B-rank Illinois No. 6 Seam; (2) a highly fluid, good coking quality, high-volatile A-rank Pittsburgh Seam; and (3) a strongly coking low-volatile Blue Creek Seam. Each lithotype sample was carbonized in small-scale (50 g) charges with each of three additives at 0, 2, 5, and 10% additive by weight. The additives included ASP, an asphalt pitch; KRP, a petroleum residue pitch; and SRC, a solvent-refined coal product. The different lithotypes were sampled to examine the effects of coal type as well as rank. A micro-tumbler test was used to give at least a relative coke-strength value for the cokes produced. In addition, all the cokes produced were examined microscopically to determine the effects of co-carbonization on the coke structure.The Illinois No. 6, Pittsburgh, and Blue Creek Seam coals all showed substantial strength increases when co-carbonized with 2, 5, and 10% of each of the three additives, particularly at the 5 and 10% levels. The SRC appears to be the best additive overall for the three ranks of coal, as judged by its ability to combine with the coal to make a higher strength coke. There appear to be no conclusive coke-strength differences among lithotype samples for any of the three coals, probably because of the small scale of the tests and the relatively small differences in inert maceral content among the lithotypes. Five percent by weight of additive appears to be sufficient, if properly blended with the coal charge, to produce higher strength cokes. This is also probably the maximum economically viable level, particularly in the United States coking industry. Two percent is probably the minimum additive level for adequate mixing on a commercial scale.  相似文献   

13.
Seams from the St. Rose and Chimmey Corner coalfields, Nova Scotia, Canada, were sampled and examined for petrographic and geochemical composition. Rank determinations indicate a rank of high volatile C-B bituminous. Seams show regular alternations of dull and bright microbanded lithotypes, with dull lithotypes predominant in the central portion of the main seam (No. 5 seam). Brighter lithotypes are dominated by vitrinite (>80%), with minor inertinite (avg. 12%) and minor liptinite. Duller lithotypes contain greater amounts of inertinite (up to 40%) and liptinite (primarily sporinite). Mineral matter consists of epigenetic pyrite, with lesser amounts of clay and quartz. Cabonates are common in the Chimney Corner seams. Elemental composition of the seams is similar to other Canadian coals and fall within world coal ranges, with the exception of high concentrations of Cl, Zn, Ni, Mo, Pb, Cu and As.Depositional environment of the seams as indicated by maceral composition, lithotypes and geology suggest a predominance of wet forest to reed moor conditions, in a fluvial-lacustrine setting. Periodic episodes of flooding and drying are indicated by lithotype, maceral and mineral variations.  相似文献   

14.
The Liddell Seam occurs in the lower part of the Permian Foybrook Formation of the Sydney Basin, eastern Australia. The seam profile is dominated by banded lithotypes (clarain). Maceral and microlithotype analyses of lithotypes indicate a limited degree of uniformity in their composition. A comparison of whole-seam petrographic analyses with compositions calculated on the basis of the seam lithotype profile and lithotype petrography suggests that the latter method may provide for a rapid assessment of petrographic variation in operating mines.Petrographic analyses form the basis of an interpretation of Liddell peat-swamp facies. The seam contains few clastic layers which are associated with relatively dull coals whose petrography reflects elevated water levels during deposition in the limno-telmatic, reed-moor and open-moor facies. Between these zones the seam profile is dominated by relatively bright coals deposited between periods of inundation, in the telmatic forest-moor and reed-moor zones. The lithotype profile and the high vitrite and clarite content indicate the significant influence of arborescent vegetation, a feature typical of seams deposited in tectonically unstable areas.  相似文献   

15.
A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and13C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.  相似文献   

16.
Two major earthquakes occurred on October 23rd, 2011 (M=7.1) and November 9th, 2011 (M=5.6) in Tabanli and Edremit districts of Van province in Turkey, respectively. New settlement areas for Van city were determined after these destructive earthquakes. One of the most important areas for new settlements to be built was Edremit region, consisting travertine where nearly 80% of new housing units (12.384) were built by TOKI (Housing Development Administration of Turkey). Travertines have different lithotypes depending on their depositional process such as crystalline crust, shrub, reed which can affect mechanical and engineering properties of travertine and each level has different handicaps. The purpose of this study is to investigate the relationship between lithotype and physico-mechanical properties of travertines. According to the results, lithotype has an effect on physical, mechanical and rock mass properties of travertine. It is ascertained by several research methods that various handicaps may occur on such areas when the active tectonic structure of the area is evaluated along with the karstic cavities within the travertine and different lithotype qualities.  相似文献   

17.
In the Leão-Butiá Coalfield, Rio Grande do Sul the coal seams occur in the Rio Bonito Formation, Guatá Group, Tubarão Supergroup of the Paraná Basin, Brazil and are of Permian (Artinskian–Kungurian) age.This study is the first detailed investigation on the coal petrographic characterization of the coal-bearing sequence in relation to the depositional settings of the precursor mires, both in terms of whole seam characterization and in-seam variations. The study is based on the analyses of nine coal seams (I2, CI, L4, L3, L2, L1, S3, S2, S1), which were selected from core of borehole D-193, Leão-Butiá and represent the entire coal-bearing sequence.The interpretation of coal facies and depositional environment is based on lithotype, maceral and microlithotype analyses using different facies-critical petrographic indices, which were displayed in coal facies diagrams. The seams are characterized by the predominance of dull lithotypes (dull, banded dull). The dullness of the coal is attributed to relatively high mineral matter, inertinite and liptinite contents. The petrographic composition is dominated by vitrinite (28–70 vol.% mmf) and inertinite (> 30 vol.% mmf) groups. Liptinite contents range from 7 to 30 vol.% (mmf) and mineral matter from 4–30 vol.%. Microlithotypes associations are dominated by vitrite, duroclarite, carbominerite and inertite. It is suggested that the observed vertical variations in petrographic characteristics (lithotypes, microlithotypes, macerals, vitrinite reflectance) were controlled by groundwater level fluctuations in the ancient mires due to different accommodation/peat accumulation rates.Correlation of the borehole strata with the general sequence-stratigraphical setting suggests that the alluvial fan system and the coal-bearing mudstone succession are linked to a late transgressive systems tract of sequence 2. Based on average compositional values obtained from coal facies diagrams, a deposition in a limno-telmatic to limnic coal facies is suggested.  相似文献   

18.
Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state 13C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.  相似文献   

19.
Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ13C, δ15N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS 13C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.  相似文献   

20.
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.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号