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1.
Variation in the degree of aromatic condensation of chars   总被引：1，自引：0，他引：1  
Char is ubiquitous in the environment and contributes significantly to the inert soil organic carbon pool. Its roles as a carbon sink and a strong sorbent of organic contaminants have come under increasing attention. However, quantifying these roles is difficult because properties such as degradability and sorption affinity vary greatly amongst chars, especially those produced at different temperatures. Here we describe a simple method for gauging the degree of aromatic condensation of chars, a molecular-scale property that affects both their degradability and sorption affinity. The method involves adding 13C6 benzene directly to char. The 13C nuclear magnetic resonance (NMR) chemical shift of the sorbed benzene is affected by diamagnetic ring currents in the fused aromatic structures in the char. These ring currents increase in magnitude with increasing extent of aromatic condensation. Seventeen heat-treated materials were analysed in this way. Our results confirm that aromatic condensation increases with increasing heat treatment temperature (HTT) and that activated chars contain the most highly condensed aromatic structures, but also show the importance of starting material and heat treatment time on aromatic condensation. We also show for four of the materials that the ring current effect on chemical shift was similar for other 13C-labelled molecules, including MeOH, CH3CN and toluene.  相似文献   

2.
Quantifying the role of black carbon (BC) in geochemical processes is difficult due to the heterogeneous character of its chemical structure. Chestnut wood charcoal samples produced at heat treatment temperatures (HTT) from 200-1000 °C were analysed using two different solid state 13C NMR techniques. First, aromaticity was determined as the percentage of total signal present in the aromatic region of 13C direct polarisation (DP) spectra. This was found to increase through the low temperature range of 200-400 °C; at higher temperatures, aromaticity was found to be >90%. Second, aromatic condensation was determined through the measurement of the chemical shift of 13Cbenzene sorbed to the charcoals, which is influenced by the presence of “ring currents” in the aromatic domains of the charcoals. This technique was less sensitive to molecular changes through the lower temperature range, but showed there was a smooth increase in the degree of condensation of the aromatic structures with increasing temperature through the temperature range 400-1000 °C. Ab initio molecular modelling was used to estimate the size of aromatic domains in the charcoals based on the strength of the ring currents detected. These calculations indicated that charcoals produced at temperatures below 500 °C contain aromatic domains no larger than coronene (7 ring). At higher temperatures the size of these domains rapidly increases, with structures larger than a 19 ring symmetrical PAH being predominant in charcoals produced at temperatures above 700 °C. Data from this study were found to be generally consistent with previously published measurements using the benzenepolycarboxylic acid (BPCA) molecular marker method on the same set of samples.  相似文献   

3.
Vegetation fires play a major role in global C cycling through the addition of inert carbon (char) to the environment. The objective of this study was to compare and contrast the chemical composition of 53 natural chars collected from the soil surface 6–32 years after a natural fire. In order to achieve this, we applied a recently developed nuclear magnetic resonance (NMR) technique that gauges the degree of condensation of aromatic structures within chars. Our results show that the degree of condensation varied considerably among char samples (n = 4–5), collected from burnt-out tree stumps at each of the 11 fire sites. This demonstrates that there is a great degree of variability in the composition of the char produced in natural fires, which is likely to be reflected in widely varying rates of char decomposition. This highlights a major difficulty in quantifying the effects of vegetation fires on global C cycling. Importantly, no differences could be discerned between chars of different ages, indicating that ageing of this type of char in this environment is slow on the decadal timescale. Finally, this study demonstrates that although char samples appear to preserve a record of fire conditions, great care must be taken when interpreting this record to account for the high degree of heterogeneity in char composition. Bulking of char samples would alleviate this problem to some extent; however, bulking would mask the inter-particle heterogeneity clearly evident in this study.  相似文献   

4.
A recent comparative exercise found that different black carbon (BC) quantification methods produced widely varying results for a set of BC reference materials that included three laboratory-produced BC-rich materials, five environmental BC matrices and four samples of non-BC organic matter. This variation was attributed to a range of physical and chemical properties of the samples that could, in various ways, result in the over- or under-detection of BC in some or all of the techniques. Here the most pertinent chemical and physical characteristics of the samples are presented, including elemental analysis, lightness measurements, BET surface area measurements and 13C NMR analysis. Amongst the BC-rich materials, soot and char could be distinguished from one another mainly on the basis of H/C and O/C ratios, NMR observability and BET surface area. The results indicate that the aromatic structures in the soot are more highly condensed, and this explains why some BC quantification techniques detect these two materials differently. The non-BC potentially interfering materials were shown to share properties with the BC-rich materials (high C content, low lightness values and high aromaticity) that are used for certain BC quantification methods. This may lead to overestimation of BC unless these interfering materials are removed during pre-treatment. The environmental matrices were found to have relatively high amounts of metal oxides that have the potential to catalyse or inhibit thermal and chemical reactions during BC analysis.  相似文献   

5.
高磁场固态碳13核磁共振法研究干酪根的热降解成烃机理   总被引：3，自引：0，他引：3  
用高磁场(75.46MHZ)固态碳13核磁共振(NMR)波谱仪研究了抚顺油页岩在热降解模拟试验中干酪根的化学结构变化.为了消除旋转边带的干扰,在应用交叉极化与魔角自旋(CP/MAS)技术的同时,采用了Dixon TOSS技术,从而得到高分辨的波谱图。据此测定了热降解过程中干酪根各种碳结构组成的变化,计算了芳碳率、亚甲基基团平均碳原子数、环缩合指数等一系列干酪根的结构参数,并与干酪根的相对产油潜力相关联.发现干酪根的产油潜力直接与亚甲基基团的含量有关,而芳碳以及与芳碳相连的甲基碳则贡献甚微.文中还对干酪根的热降解成烃机理作了探讨。  相似文献   

6.
The significance and validity of integrating data obtained from a variety of analytical techniques to understand, elucidate and model kerogen's complex chemical structure is reported here using degradative (open and closed system pyrolysis, chemical oxidation), non-degradative (13C CP/MAS NMR) and optical (incident white light and blue light) methods. Seven Cambrian Alum Shale samples, ranging in maturity from immature to post-mature with respect to petroleum generation, were studied and were chosen for their simple geological history, uniform organic matter type and high organic carbon content. The Alum Shale kerogens, which primarily consist of algal organic matter, liberate low molecular weight gaseous and aromatic compounds on pyrolysis and give mostly branched dicarboxylic acids on chemical oxidation. 13C NMR spectroscopy shows that the Alum Shale kerogens are anomalously rich in oxygen-bearing functional groups (such as C = O, ArCO, CHO, CHxO), most of which apparently remain intact within the kerogen macro-molecule (KMM) through the diagenetic and catagenetic stages. Fragments released by different degradative techniques are quantified and the aromaticity (fa), O/C and relative proportions of various carbon types estimated by 13C NMR. A synthesis of these data has allowed us to better understand the chemistry of the Alum Shale kerogen.  相似文献   

7.
Core drilling of near surface seams near Wakefield NSW has provided high volatile bituminous coal samples that have been subject to varying degrees of natural in situ oxidation. Five levels of oxidation have been defined, mainly on visual evidence, ranging from unoxidised coal to highly oxidised material. Samples of each oxidation level have been investigated by chemical analysis, Fourier transform infrared spectroscopy (FTIR) and solid state carbon-13 nuclear magnetic resonance spectroscopy (NMR) with cross-polarization and magic angle spinning.The results show that mineral matter, moisture and oxygen content increase with oxidation, whereas carbon, hydrogen and specific energy decrease. Moisture determination is suggested as a quick, facile method for indicating the oxidation level for a coal sample from this seam. FTIR showed a marked loss of aliphatic C-H groups with increasing oxidation, and an increase in carbonyl and carboxylate groups. Aromatic C-H groups were much less affected by oxidation. Solid state carbon-13 NMR showed increasing carbon aromaticity with oxidation, but showed substantial carbonyl carbon only at the highest oxidation level. No evidence was found for an increase in aromatic substituents during oxidation; if anything, there is a small decrease in substituents.  相似文献   

8.
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   

9.
超临界CO2对煤化学结构的改造对煤层CO2封存能力极为关键。论文开展了模拟埋深1500m （62.5℃、15 MPa）条件下4组不同变质程度煤的ScCO2-H2O体系与煤岩地球化学反应实验。通过傅里叶变换红外光谱和X射线粉末衍射实验获得了反应前后煤化学结构演化特征,探讨了煤化学结构演化的机理。结果表明:ScCO2作用后,煤中脂肪烃链长度普遍增加,仅肥煤的芳香烃丰度增大,肥煤、瘦煤和贫煤含氧基团丰度的增大主要由氢键基团含量的增加贡献,无烟煤含氧基团丰度则主要受低分子化合物溶出的影响。ScCO2引起的溶胀作用造成肥煤和瘦煤芳香层面之间交联键断裂,芳香微晶内部结构疏松,而芳香层面内CAr-CAr交联的形成提高了肥煤和瘦煤芳香性和芳香环缩合度;贫煤和无烟煤中非稠合多苯结构脱落使芳香微晶内部更紧凑,脂肪烃链长度的增加则降低了贫煤和无烟煤芳香性和芳香环缩合度。   相似文献   

10.
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   

11.
Samples of heat affected coal taken near two igneous intrusions (dykes) in the Victoria Tunnel Seam of the Newcastle Coalfield have been investigated by chemical analysis, petrography, Fourier transform infrared spectroscopy and solid state13C NMR spectroscopy. Visual inspection of the seam near the intrusion showed four distinct zones. These have been called, in order of increasing distance from the dyke, the massive cinder, the banded cinder, heat affected coal and apparently unaffected coal. The samples show an increase in structural change as the distance from the dyke decreases, with the samples taken from the massive cinder nearest the dyke being classified as semicokes.FTIR and13C NMR results, together with the results of dipolar dephasing NMR experiments, suggest that the predominant structural change in the heat affected zone is replacement of aromatic ethers and/or phenols with hydrogen, leading to an increase in proton aromaticity. Closer to the intrusion, bond rupture leads to a marked loss of aliphatic groups, while in the most affected region adjacent to the dyke aromatic crosslinking has also occurred to form coke-like material.  相似文献   

12.
《Applied Geochemistry》2006,21(7):1226-1239
Natural organic matter (NOM) from the Han River, Korea was fractionated into humic and non-humic fractions by absorbing onto XAD-7HP, and these fractions were analyzed using UV-absorption, and for dissolved organic C (DOC). The humic fraction (i.e. humic substances; HS) was extracted and its characteristics were compared to commercial humic materials using various spectroscopic methods such as Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H-NMR) and fluorescence spectroscopy. The humic fraction as organic C was 47.0% on the average, however, a rainfall event brought a higher humic fraction into Han River water. The molar ratios of H/C and O/C in the HS from Han River water (HRHS) were 1.40 and 0.76, respectively, and the ratio of aliphatic to aromatic protons in the HS (PAl/PAr ratio) was 5.8. Aromaticity and humification degree (i.e., degree of condensation) of HRHS were relatively lower than those from other humic materials, while the portion of oxygenated functional groups was relatively higher. FT-IR, 1H-NMR and fluorescence spectroscopy showed distinct differences between HRHS and the commercial humic materials. Commercial humic materials are not representative of HS extracted from Han River water. The fluorescence spectra, relatively simple measurements, were found to be most useful as fingerprints for humic materials from particular sources.  相似文献   

13.
Previously studied thermosequences of wood (chestnut) and grass (rice straw) biochar were subjected to hydrogen pyrolysis (hypy) to evaluate the efficacy of the technique for determining pyrogenic carbon (CP) abundance. As expected, biochar from both wood and grass produced at higher temperature had higher CP amount. However, the trend was not linear, but more sigmoidal. CP/CT ratio values (CT = total organic carbon) for the wood thermosequence were ⩽0.03 at biochar production temperature (TCHAR) ⩽ 300 °C. They increased dramatically until 600 °C and remained relatively constant and near unity at higher biochar production temperature. Grass biochar was similar in profile, but CP/CT values rose dramatically after 400 °C. The findings are consistent with the hypothesis that hypy residues contain polycyclic aromatic hydrocarbons (PAHs) with a degree of condensation above at least 7–14 fused rings, with labile organic matter and pyrogenic PAHs below this degree of condensation removed by hypy.Both wood and grass thermosequences displayed δ13CP values that decreased with increased TCHAR, indicating that recalcitrant carbon compounds (pyrogenic aromatic PAHs with a relatively high degree of condensation) were first formed from structural components with relatively high δ13C values (e.g. cellulose). Relatively constant δ13C values at TCHAR ⩾ 500 °C suggested the dominant pyrolysis reaction was condensation of PAHs with no additional fractionation. Comparison of hypy with benzene polycarboxylic acid (BPCA), ‘ring current’ NMR and pyrolysis gas chromatography–mass spectrometry (GC–MS) results from the same suite of samples indicated a consistent overview of the structure of CP, but provided unique and complimentary information.  相似文献   

14.
We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as “oil prone” and “gas prone” carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (∼30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ∼30 carbons, and of ∼20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters.  相似文献   

15.
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   

16.
The structural, spectroscopic and phenanthrene binding characteristics were compared for humic acids (HA) extracted from two different sources: eight soils and six lake sediments. The elemental analysis revealed that HA from sediments had higher H/C, N/C, and (N + O)/C ratios compared to HA from soils, reflecting a lower degree of humification and more autochthonous organic input upon the formation of the HA for lake sediments versus soil environments. HA from soils exhibited a higher content of aromatic carbon structures than the sediment HA based on 13C NMR results. The source of HA was easily distinguished by comparing the synchronous fluorescence spectra of each HA group. The presence of a protein like fluorescence was prominent for the HA from sediment while it was minor for the HA from soil. Irrespective of the HA source, however, humification index (HIX) exhibited a common positive correlation with the aromatic content, and a negative correlation with O-alkyl carbon structures of the HA. The correlations were consistent with the general structural trends of humification processes, suggesting that HIX may serve as a source independent predictor to describe the structural information and humification degree of terrigenous HA. Aromatic carbon structures did contribute to enhancing the phenanthrene binding for both sources of HA. However, the primary structures associated with non-ideal phenanthrene binding (i.e., non-linear sorption isotherm) appear to differ by the HA source because the opposed correlations were obtained between aromaticity and the isotherm linearity for the two HA groups. Our results suggest that the HA structural function associated with specific non-linear sorption for hydrophobic organic contaminants (HOCs) may be more strongly governed by the HA source than by the apparent physico-chemical properties.  相似文献   

17.
Solid bitumen can arise from several reservoir processes acting on migrated petroleum. Insoluble solid organic residues can form by oxidative processes associated with thermochemical sulfate reduction (TSR) as well as by thermal chemical alteration (TCA) of petroleum. TCA may follow non-thermal processes, such as biodegradation and asphaltene precipitation, that produce viscous fluids enriched in polar compounds that are then altered into solid bitumens. It is difficult to distinguish solid bitumen formed by TCA from TSR since both processes occur under relatively high temperatures. The focus of the present work is to characterize solid bitumen samples associated with TSR- or TCA-processes using a combination of solid-state X-ray Photoelectron Spectroscopy (XPS), Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES), and 13C NMR. Naturally occurring solid bitumens from three locations, Nisku Formation, Brazeau River area (TSR-related); La Barge Field, Madison Formation (TSR-related); and, the Alaskan North Slope, Brooks Range (TCA-related), are compared to solid bitumens generated in laboratory simulations of TSR and TCA.The chemical nature of solid bitumens with respect to organic nitrogen and sulfur can be understood in terms of (1) the nature of hydrocarbon precursor molecules, (2) the mode of sulfur incorporation, and (3) their concentration during thermal stress. TSR-solid bitumen is highly aromatic, sulfur-rich, and nitrogen-poor. These heteroatom distributions are attributed to the ability of TSR to incorporate copious amounts of inorganic sulfur (S/C atomic ratio >0.035) into aromatic structures and to initial low levels of nitrogen in the unaltered petroleum. In contrast, TCA-solid bitumen is derived from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. TCA-bitumens from the Brooks Range have <75% aromatic carbon. TCA-bitumens exposed to greater thermal stress can have a higher aromaticity, like that observed in TSR-bitumens. Organic sulfur in TCA-organic solids remains relatively constant with increasing maturation (S/C atomic ratio <0.035) due to offsetting preservation and H2S elimination reactions. Although S-XANES and 13C NMR provide information needed to understand changes in structure and reactivity that occur in the formation of petroleum solids, in some cases XPS analysis is sufficient to determine whether a solid bitumen is formed by TCA or TSR.  相似文献   

18.
Combustion produces a complex mixture of polycondensed aromatic compounds known as black carbon (BC). Such products can become remobilized from char and soil in the form of dissolved BC (DBC). Ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (ESI–FT-ICRMS) analysis of a variety of soil and char leachates showed that a significant proportion of DBC compounds contained one or more nitrogen atoms. While the presence of black nitrogen (DBN) in dissolved organic matter (DOM) has been reported, its molecular features were uncharacterized. Here we present results of FT-ICRMS characterization of DBN, where assigned formulae were validated on the basis on their 13C isotope signatures and fragmentation patterns obtained via collision induced dissociation. Possible chemical structures were assigned for several DBN formulae and suggest that nitrogen was incorporated into the core ring system as a pyrrole-type moiety. Most DBN compounds existed as part of homologous series where homologs differed by a mass corresponding to CO2, suggesting that they were polysubstituted with carboxylic acid groups. The environmental contribution of such novel, aromatic, combustion-derived nitrogen compounds with respect to global nitrogen cycling remains elusive. The biogeochemical implications of the input of such fire-derived products to aquatic ecosystems as part of climate change therefore need to be assessed.  相似文献   

19.
《Geochimica et cosmochimica acta》1999,63(11-12):1805-1813
A comparison of two independent techniques was used to assess the homogeneity of CO2 and H2O concentrations in a number of natural basaltic glasses. Variations in carbon concentration and isotopic ratio were determined by comparison of stepped heating data obtained in two different laboratories. Dissolved volatile concentrations were also obtained by stepped heating and Fourier Transform Infrared (FTIR) spectroscopy. Replicate stepped heating analyses of a mid-ocean ridge basaltic glass show that the concentration and 13C/12C of bulk magmatic and dissolved CO2 vary by less than ±10% and ±0.5‰, respectively. A similar degree of correlation is observed for replicate stepped heating analyses of Mariana Trough glasses conducted in two different laboratories. Dissolved CO2 concentrations determined by stepped heating also correlate well with concentrations measured by FTIR spectroscopy. The correspondence of results obtained in these experiments provide an upper limit to the degree of natural variation in concentrations and isotopic ratios of these volatiles in basaltic glasses and suggest that intrinsic, magmatic carbon has a relatively homogeneous distribution in these glasses. Water concentrations determined through extraction by heating and FTIR also show excellent agreement.  相似文献   

20.
Silicon carbide (SiC) is a particularly interesting species of presolar grain because it is known to form on the order of a hundred different polytypes in the laboratory, and the formation of a particular polytype is sensitive to growth conditions. Astronomical evidence for the formation of SiC in expanding circumstellar atmospheres of asymptotic giant branch (AGB) carbon stars is provided by infrared (IR) studies. However, identification of the crystallographic structure of SiC from IR spectra is controversial. Since >95% of the presolar SiC isolated from meteorites formed around carbon stars, a determination of the structure of presolar SiC is, to first order, a direct determination of the structure of circumstellar SiC. We therefore determined the polytype distribution of presolar SiC from the Murchison CM2 carbonaceous meteorite using analytical and high-resolution transmission electron microscopy (TEM). High-resolution lattice images and electron diffraction of 508 individual SiC grains demonstrate that only two polytypes are present, the cubic 3C (β-SiC) polytype (79.4% of population by number) and the hexagonal 2H (α-SiC) polytype (2.7%). Intergrowths of these two polytypes are relatively abundant (17.1%). No other polytypes were found. A small population of one-dimensionally disordered SiC grains (0.9%), whose high density of stacking faults precluded classification as any polytype, was also observed. The presolar origin of 2H α-SiC is unambiguously established by tens-of-nanometers-resolution secondary ion mass spectroscopy (NanoSIMS). Isotopic maps of a TEM-characterized 2H α-SiC grain exhibit non-solar isotopic compositions of 12C/13C = 64 ± 4 and 14N/15N = 575 ± 24. These measurements are consistent with mainstream presolar SiC thought to originate in the expanding atmospheres of AGB carbon stars. Equilibrium condensation calculations together with inferred mineral condensation sequences predict relatively low SiC condensation temperatures in carbon stars. The laboratory observed condensation temperatures of 2H and 3C SiC are generally the lowest of all SiC polytypes and fall within the predictions of the equilibrium calculations. These points account for the occurrence of only 2H and 3C polytypes of SiC in circumstellar outflows. The 2H and 3C SiC polytypes presumably condense at different radii (i.e., temperatures) in the expanding stellar atmospheres of AGB carbon stars.  相似文献   

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