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1.
The distribution of aromatic hydrocarbons and stable carbon isotope ratios of organic matter in a series of nine Miocene Embalut coal samples obtained from nine coal seams of Kutai Basin, East Kalimantan, Indonesia were studied. The rank of the Embalut coals ranged from lignites to low rank sub-bituminous coals (0.36–0.50% Rr), based on measurements of huminite reflectance. The aromatic hydrocarbon fractions of all coal samples were dominated by cadalene in the lower boiling point range and picene derivatives in the higher boiling point range of the gas chromatograms. Cadalene can be attributed to the contribution of Dipterocarpaceae and various hydrated picenes to the contribution of additional angiosperms to the coal forming vegetation. The picenes originate from alpha- and beta-amyrin. However, in some coal samples minor amounts of simonellite and retene were also detected which argues for an additional contribution of gymnosperms (conifers) to coal forming vegetation preferentially in the Middle Miocene and at the beginning of the Late Miocene. The results of stable carbon isotope ratios (δ13C) in most of the coal samples are consistent with their origin from angiosperms (δ13C between ?27.0‰ and ?28.0‰). During the Miocene the climate of Mahakam Delta was not uniformly moist and cooler than the present day climate. This would have been favourable for the growth of conifers, especially in the montane forests. The contribution of conifers to the Embalut coals might be a result of the cool Middle/Late Miocene climate during peat accumulation in the Kutai Basin.  相似文献   

2.
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.  相似文献   

3.
The recent development of “second generation” NMR experiments on coals is discussed in this paper. Such experiments have three aims: (1) To determine the extent to which quantitative aromaticity measurements can be made on coals by cross polarization-magic angle spinning (CP/MAS); (2) To obtain more detailed information on coal structure and reactivity than that given by the simple aromaticity measurements possible at the time; (3) To follow reaction pathways when coal is chemically modified. In this plenary lecture the relevant literature is reviewed, and new experimental work in all three areas outlined above is reported. Experimental evidence is presented which shows that aromaticity measurements on a bituminous coal by cross polarization (CP) or single pulse techniques give identical results. Relaxation data for naphthalene polymers suggest that these structures in coal are seen in CP experiments. Dipolar dephasing experiments suggest that the average size of the coal vitrinite molecule does not increase with increase in coal rank due to aromatic substitution reactions. Various relaxation experiments demonstrate how different carbon types can be distinguished in both13C-labelled and unlabelled coals.  相似文献   

4.
The Mahakam delta (Kalimantan, Indonesia) coals represent all the evolution stages between freshly-deposited plant/peat material, lignites and bituminous coals. The geochemical techniques used to study this coal series included elemental analysis, extraction of humic compounds, infrared spectroscopy and 13C nuclear magnetic resonance of the total coal.The main mechanisms of early maturation in this series are loss of oxygenated compounds, aromatisation and condensation of the organic matter. These changes, which have already been suggested for other coal series and partially reported for sedimentary organic matter, were confirmed and described in more detail for the Mahakam coal series.  相似文献   

5.
Thermal transformations of kaolinite of different degree of crystallinity have been monitored by 27Al and 29Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. 29Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q 3 symmetry just above the onset of dehydroxylation and the Q 4 environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q 4 silicons) and a faint resonance, from mullite, at ca. -87 ppm. 29Si NMR also shows that cristobalite germs are already present at 950–1000° C. The 27Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the 27Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.  相似文献   

6.
The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from Corg-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC2–3 to MC1–2. The 13C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.  相似文献   

7.
Black carbon (BC) is an important residue of wildfires in boreal forests, but its characteristics depend on its formation conditions. The objective of this study was to characterize the chemical and physical properties of BC produced under controlled laboratory conditions, while mimicking a gradient of wildfire severity. We used fuels originating from mosses, ericaceous shrubs and spruce trees, as they constitute the major types available in boreal forests. We varied the maximum temperature (MT) from 75 to 800 °C, the duration of charring from 0.5 to 24 h and the abundance of O2. BC properties were analyzed using elemental analysis and proximate analysis, solid state 13C nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM) and surface area (SA) analysis. MT was the most significant factor affecting both chemical and physical changes. Results from 13C NMR spectroscopy indicated that 350 °C was a threshold temperature, above which spectra became dominated by aromatic structures for all fuels. Charring duration affected BC composition at both low (250 °C for 12 h vs. 24 h) and high (600 °C for 0.5 h vs. 6 h) MT. The presence of O2 influenced BC composition mainly at low MT (250 °C) and resulted in accelerated alkyl C degradation, accompanied with a distinct decrease in yield. Results from the SA analysis and the SEM micrographs showed that fuel type influenced BC physical properties, with moss-derived BC presenting higher surface area and microporosity than BC of woody origin.  相似文献   

8.
To obtain information on the contribution of aromatic fragments to the chemical structure of humic substances, we carried out a study on the [1H]NMR and [13C]NMR spectra of humic and fulvic acids and their oxidative degradation products extracted from an Andosol soil.[1H]NMR spectra of all organic fractions present considerable adsorption between 7.4 and 8.8 ppm, due to the presence of aromatic protons.The percentages of aromatic protons in respect to the total amount of protons are as follows: FA 20%, HA 19%, degraded FA < 12%, degraded HA 14%. The values indicate that the contribution of aromatic structures to the humic substances is significant, also considering that they are highly substituted.The degraded fractions contain smaller amounts of aromatic protons, because degradation causes the opening of the aromatic rings. Thus results obtained from the degradation do not seem to be reliable for defining the importance of aromatic structures in humic substances.Also the [13C]NMR spectra show signals in the aromatic region which derive from unsubstituted carbon atoms, while signals originating from tertiary carbon atoms merge with the noise. We believe that, at present, [1H]NMR spectroscopy is more suited for studying the role played by aromatic compounds in organic soil fractions.  相似文献   

9.
Dynamics of catagenetic changes in the structure of humic coals in the Earth's interior can quantitatively be described using X-ray indices of components (phases), redistribution of which is determined by a system of differential equations in geological time. The system describes changes in the main formation parameters of coal seams in the Earth's interior (subsidence depth, temperature, pressure, and catagenesis index), on the one hand, and kinetics of catagenetic transformation of organic matter (OM), on the other. Such model makes it possible to establish regular changes in the phase composition of humic coals at different stages of coal basin formation. Using Paleozoic (Middle Carboniferous) coals of the Donets Basin as an example, it is established that main changes in the OM structure took place during the maximal subsidence of coal seams at maximal temperatures ranging from 110–15°C (for slightly metamorphosed coals of the L and G ranks) to 28°C (for anthracites) and pressures ranging from 55–74 to 146 MPa, respectively. Major processes leading to the observed X-ray phase composition of coals during the maximal subsidence of sedimentary sequences lasted approximately 40 Ma regardless of the geological age of sediments (Middle Carboniferous or Permian coal seams of the Donets or Kuznetsk coal basins, respectively).  相似文献   

10.
Solid-state 27Al, 29Si and 23Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and 29Si NMR data have previously been reported. 27Al δi vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the 29Si chemical shifts assigned to the T2m-site. The 27Al and 29Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]1b. The linewidths of the 29Si and 27Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average 23Na δi varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average 23Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution 23Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the 23Na NMR lineshape of Or49 after short periods of heat treatment indicate that 23Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.  相似文献   

11.
D/H, 13C/12C, 18O/16O and 34S/32S ratios in the organic matrix and organic solvent extracts of Australian coals, and in the fluids and minerals associated with these coals, are reported and reviewed against similar isotopic data for coals from other regions.Where coals are immature, original isotopic differences between macrolithotypes, and between solvent extracts (lipid concentrates) and insoluble residues, are largely preserved. However, with increasing maturity these characteristic differences, particularly those between macrolithotypes, are rapidly erased. Conversely, where, as indicated by low total sulfur contents, coals of Cretaceous to Permian age were deposited under essentially freshwater conditions, δ34S values* for the organically-bound sulfur remain remarkably constant at +4 ± 3‰ relative to meteoritic sulfur. In similar, younger Tertiary coals, the organic sulfur is markedly enriched in 34S.Five distinctive isotopic patterns, which may be interpreted in terms of the environment of sulfate reduction, can be recognized from 34S/32S ratio measurements on the various forms of sulfur in Australian coals.Isotopic studies of seam gas hydrocarbons collected in situ show these to be unexpectedly strongly depleted in the heavier isotopes of hydrogen and carbon relative to natural gases from proposed humic sources. Furthermore, no pronounced increase in the 13C content in methane with increase in rank of the parent coal was observed. In addition, several sources of associated carbon dioxide have been delineated, including normal maturation processes, invasion of the seams by magnetic carbon dioxide, and interaction of the coal with intrusive magma.Isotopic exchange between free seam gases is not accepted as an explanation for some unusual isotopic fractionations seen, rather the data suggest that these gases may be formed in a state approaching isotopic equilibrium. This argument also satisfactorily explains the isotopic compositions of primary siderite and secondary calcite associated with bituminous coal seams. However, where seams are invaded and permeated with externally derived carbon dioxide, usually of magnetic origin, carbonates are frequently absent, presumably as a result of the action of carbonic acid.  相似文献   

12.
Leping coal (including barkinite-rich coal) is a unique kind of coal,which is widely distrbuted in the Late Permian Longan Formation,South China,In this paper,ROck-Eval,Py-GC and simulation experiment via an open-system were used to study the hydrocarbon-generating potential,hydrocarbon composition.and hydrocarbon-generating model of barkiniterich coals from the shuicheng coal field of Guizhou Province,Southwest China.The results show that barkinite-rich coals have high hydrocarbon-generating potential,with S1 S2 being 211-311mg/g,and can produce large amounts of hydrocorbon at the high-maturity stage,mostly within the temperature range of 420-450℃(corresponding to VR0 1.1-1.5%);barkinite-rich coal is one of the better oil sources and light hydrocarbon and wet gas are the major hydrocarbon components,which account for 45% and 33% of the total hydrocarbons.respectively.These characteristics are of importance for exploring oil and gas resources in the Late permian Longtan Formation coals,southwest China.  相似文献   

13.
Black carbon (BC) is considered ubiquitous in soil organic matter (OM) and therefore plays an important role in soil biogeochemistry. Its complexity, particularly within environmental matrices, presents a challenge for research, primarily as a result of techniques which may favor detection of certain functional group types rather than capturing total sample C. The objective of this study was to utilize carbon (C) 1s near edge X-ray absorption fine edge structure (NEXAFS) spectroscopy to characterize the C chemistry of a broad range of BC materials. Characteristic resonances in the NEXAFS spectra allowed direct molecular speciation of the total C chemistry of the reference materials, environmental matrices and potentially interfering materials, obtained from an earlier BC ring trial. Spectral deconvolution was used to further identify the functional group distribution of the materials. BC reference materials and soils were characterized by a large aromatic C region comprising around 40% of total absorption intensity. We were able to distinguish shale and melanoidin from BC reference materials on the basis of their unique spectral characteristics. However, bituminous coal shared chemical characteristics with BC reference materials, namely high aromaticity of more than 40% identified by way of a broad peak. Lignite also shared similar spectra and functional group distributions to BC reference materials and bituminous coal. We compared the results of spectral deconvolution with the functional group distributions obtained by way of direct polarization magic angle spinning (DPMAS) 13C nuclear magnetic resonance (NMR) spectroscopy. Correlations between aromatic type C values for DPMAS 13C NMR and NEXAFS gave r2 = 0.633 (p < 0.05) and the values for NEXAFS were around 30–40% lower than for 13C NMR. Correlations were also drawn between the aromatic C/O-alkyl C ratio values for the two methods (r2 = 0.49, p < 0.05). Overall, NEXAFS was applicable for a wide range of environmental materials, such as those measured, although some limitations for the technique were addressed.  相似文献   

14.
Alteration phenomena affecting organic matter during diagenesis frequently lead to the formation of residues almost insoluble. Data from 13C CP/MAS nuclear magnetic resonance analyses (NMR) of these residues have been compared to those obtained by other techniques such as elemental analysis, infrared spectroscopy, Rock-Eval pyrolysis or gas chromatography. Three examples of alteration phenomena have been chosen: the artificial and natural oxidation of coals, the biodegradation of oils and solid bitumens, and the radiolytic degradation of organic matter. NMR results and those obtained by other techniques converge on similar general conclusions. Additional information can be extracted from 13C NMR data: e.g. definition of the phenol/carbonyl ratio, transformation of the aromatic network and aromatic ring substitution. These comparisons are good evidence for the reliability of non-destructive analysis of the insoluble fraction of altered organic material by 13C CP/MAS NMR.  相似文献   

15.
MX-1 tridymite is one of the room-temperature polymorphs of SiO2 tridymite and has an underlying monoclinic structure (Cc) with incommensurate modulations along a * and c * (Hoffmann et al. 1983; Löns and Hoffmann 1987). With increasing temperature up to 500° C, MX-1 is reported to experience at least five structural phase transitions. However, its structures and the relationships to other tridymite polymorphs are unclear. We present here a 29Si MAS NMR study of the room-temperature incommensurate structure of MX-1 and its structural phase transitions up to 540° C. Our results suggest that at room temperature, all the Si sites in MX-1 tridymite are in positions with similiar ∠Si-O-Si of ～150° and are consistent with the presence of two incommensurate modulations proposed by Hoffmann et al. (1983). Simulations of the spectra yield modulation amplitudes of 1.33 and 0.87 ppm, corresponding to 0.009 and 0.006 Å for Si-Si. The maximum atomic displacements along a and b due to the modulations appear to be ～0.01–0.02 Å. The structural phase transitions of MX-1 are significantly different from those of MC tridymite below 220° C. Our high temperature results confirm that MX-1 tridymite transforms to the H5 phase at about 65° C. The most important transition occurs near 110° C, where the H5 phase transforms to a phase yielding a single, narrow NMR peak, indicating the disappearance of the superstructure and possibly the onset of the dynamic averaging. The NMR lineshapes of H5 are consistent with the metrically orthorhombic unit cell and commensurate superstructure of 2a, 2b and 10c proposed by Graetsch and Flörke (1991). The phase present above 110° C is probably similar to the OC phase, but has a mean ∠Si-O-Si of ～152.0° at 113° C, 152.9° at 185° C and 154.1° at 500° C. The transitions at ～160 and 220° C for MX-1 are subtle and probably due to impurity MC. Analysis of the modulations in the OS phase of MC tridymite indicates that their amplitudes are of the order of 0.02 Å, significantly less than the value 0.3 Å proposed by Nukui et al. (1979).  相似文献   

16.
Striated structures, many of which are conical in form, are common mesoscopic features in bituminous and semi-anthracite coals of the southern Canadian Rocky Mountains. The structures are planar, conical to pyramidal in outline and are characterized by striae which radiate from a common apex and bifurcate or “horsetail” to form secondary structures on the master surface. They are up to 20 cm in length, 4 cm in width and have apical angles varying from 10° to 50°. The striated structures occur at numerous localities in both highly sheared and relatively unsheared coal seams.The conical striated structures closely resemble some shatter cones developed in fine-grained rocks, whereas the planar striated structures are somewhat similar to chevron-structured, hackle-marked joints. The pyramidal structures are apparently unique to coal. All three types of structures are considered to be the result of brittle shear fracture based on their occurrence, orientation, and morphology. The apparently restricted occurrence of the structures to coal is likely a function of the homogeneity, and low tensile and compressive strength of bituminous and semi-anthracite coals, possibly augmented by high inter- and/or intra-particle gas pressure resulting from devolatization of the coal during progressive coalification.  相似文献   

17.
This paper gives the stable carbon isotopic data in coals from the Late Namurian to Kazanian stages inthe Serteng Mt., Xishan and Huainan coalfields of the North China Platform. Its stratigraphic pattern shows that sev-eral isotopic shifts are apparent, and the large δ~(13)C negative shifts (approximately 2.5 to 3.0‰) occurred during theStephanian, Artinskian and Kazanian are observed in three Permo-Carboniferous coalfields. Those negative shifts areneither related to the coal rank and coal macerals, nor caused by the variety of peat-forming plants. The general de-crease in the δ~(13)C values of the Stephanian, Artinskian and Kazanian coals is consistent with an overall decrease inthe δ~(13)C values of ambient atmospheric CO_2 and/or a relative increase in atmospheric P_(CO2) during the coal-forming pe-riods. Therefore the authors postulate that the oxidation of peat, and the δ~(13)C-depleted CO_2 flux into the atmosphereduring the above stages may have contributed to coeval palaeoclimatic warming by way of the greenhouse effect.  相似文献   

18.
《Organic Geochemistry》1999,30(8):881-889
The 13C/12C isotopic ratios for coal-derived polycyclic aromatic hydrocarbons (PAHs) from a number of processes encompassing low and high temperature carbonisation, gasification and combustion have been determined using gas chromatography–isotope ratio mass spectrometry (δ13C GC–IRMS). The results, in conjunction with those for PAHs released under controlled laboratory pyrolysis conditions, indicate that the primary control on the isotopic values of coal-derived PAHs is likely to be the extent of ring growth required to form PAHs during processing. Thus, for relatively mild conversion processes such as low temperature carbonisation where the major aromatics are alkyl substituted 2–3 ring PAHs, the isotopic signatures are similar to those of the parent coals (−24 to −25‰ for UK bituminous coals). However, the δ13C values for the PAHs become lighter in going to high temperature carbonisation (−25 to −27‰), gasification (−27 to −29‰ for old Town gas plants in the UK) and combustion (−29 to −31‰) as the extent of ring condensation increases and confirming that the PAHs are not released as primary volatiles. To demonstrate the potential of applying these differences to source apportion environmental PAHs where major inputs from coals can be expected, soil and vegetation samples taken close to a low temperature carbonisation plant (Bolsover, North Derbyshire) have been analysed. In addition to low temperature coal tar, significant inputs of PAHs from transport fuels, high temperature carbonisation and possibly combustion (coal/biomass) have been inferred from the isotopic ratios, taken in conjunction with the differences in alkyl substitution patterns.  相似文献   

19.
This study presents data on the composition of organic matter from the Late Silurian sediments of the Chernov uplift. These sediments are characterized by low Corg contents, which may reach 1–3% in individual layers. A relatively high thermal maturity of organic matter is confirmed by polycyclic biomarker distributions and Rock-Eval pyrolyisis data. Despite its higher thermal maturity level (T max = 456°C), kerogen in carbonaceous shales from the Padymeityvis River exhibits good preservation of long-chain n-alkyl structures, which are readily identified in the 13C NMR spectra and by the molecular analysis of the kerogen pyrolysis products.  相似文献   

20.
A variety of fungal melanins with natural 15N abundance are characterized by solid-state 13C and 15N NMR spectroscopy and are compared to solid-state 13C and 15N NMR spectra of organic matter from representative soils. In all solid-state 15N NMR spectra the peptide/amide region (−220 to −285 ppm) dominates with more than 70% of the total intensity. The region between −285 and −375 ppm, assigned to amino and ammonium groups, always contains more than half of the remaining intensity. The area in the region from −30 to −220 ppm, where aromatic heterocycles would show signals, makes up less than 10% of the total intensity. These findings call into question common structural models for melanins. The solid-state 13C NMR spectra, on the other hand, reveal large differences when the melanins are compared to each other, and to composts and soils. The concentration of the aromatic carbon varies from 5 to 40% in the melanin series. The ratio Caro/Ntot and Cali/Ntot were calculated, and confirm that nitrogen in these samples is bound in Ca-groups rather than in aromatic heterocyclic structures.  相似文献   

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