Comparison of oil shales and kerogen concentrates by 13C nuclear magnetic resonance

Six oil shales and their kerogen concentrates have been studied using ¹³C CP/MAS NMR techniques to study the distribution of organic carbon species. It is found that if the aromatic and aliphatic regions are divided at about 80 or 100 ppm, the apparent aromaticities of a raw shale and its kerogen concentrate are in good agreement. The presence of oxygen-substituted carbons in the raw shales and their depletion in the kerogen concentrates are observed and discussed.     

Cross polarization magic-angle spinning 13C NMR spectra of oil shales

Cross plarization magic-angle spinning ¹³C NMR spectra have been obtained on oil shales representing a variety of geologic ages, origins, depositional environments, and source locations. The spectra show variations in the aliphatic and aromatic carbon distributions of the oil shales and reveal correlations between aliphatic carbon contents and potential shale oil yields. Hints of additional fine structure are present in the spectra of some samples, and examples are given of the spectral resolution that may be obtainable on other solid samples of geochemical interest.     

13C/12C composition, a novel parameter to study the downward migration of paper sludge in soils?

δ ¹³C values of crop and forest soils were measured 8 years after disposal of paper sewage sludge. The carbon transfer from paper sludge downward to the first humic layer is evidenced by a ¹³C-enrichnient of up to + 5.6‰ due to the input of ¹³C-enriched sludge carbonates. ¹³C/¹²C composition is thus a novel, sensitive parameter to follow the downward transfer of paper sludge carbon.     

1H and 13C NMR of marine humic acids

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.     

Carbon in olivine single crystals analyzed by the 12C(d,p)13C method and by photoelectron spectroscopy

Carbon subsurface concentration profiles in olivine single crystals from San Carlos, Arizona, and the Sergebet Island. Red Sea, containing total carbon between 60–180 wt.-ppm, were analyzed by means of the ¹²C(d. p)¹³C nuclear reaction and by x-ray induced photoelectron spectroscopy (XPS) in combination with acid etching and with Ar⁺ ion sputtering respectively, between 200–930 K. The (d, p) analysis reveals equilibrium subsurface C profiles extending 1–2 μm or more into the bulk. Their steepness is a function of temperature. Typical mean C concentrations at 300 K in the resolvable layers, 0–0.6, 0.6–1.2, and 1.2–1.8 μm. are 1.8, and 0.6 wt.-%, corresponding to enrichment factors over the mean bulk C concentration of the order of 100, 40 and 30 respectively. In the topmost atomic layers analyzed by XPS the carbon is enriched by a factor of the order of 1000, decreasing with increasing temperature. The results suggest that the carbon is in a truly dissolved state and highly mobile, subject to a reversible subsurface segregation. Most probably local lattice strain associated with the solute C species provide the driving force for this diffusional process. The C diffusion coefficient was determined from the (d, p) data below 300 K: D= 10^?13 exp(?7.8/RT) [m²· sec^?1; KJ · mole^?1] and from XPS data between 450–925 K: D = 10^?14 exp(-6/RT) [m² · sec^?1; KJ · mole^?1] The estimated error of the preexponential factors is ± one order of magnitude, that of the activation energies ±3.5 and ±2 KJ mole^?1 respectively.     

Carbon-13 cross polarized magic-angle samples spinning nuclear magnetic resonance of melanoidins

Melanoidins synthesized from amino-acids and sugars in various ratios and humic substances from Hula Basin (Israel) have been investigated by ¹³C-CP/MAS NMR spectroscopy. Most spectra indicated a significant similarity between melanoidins and humics. It is suggested that the Maillard reaction plays a more significant role in the formation of humic substances than the “traditional” theory based on a lignin source. Several heterocyclic and heteroaromatic moieties (mainly furanoid, hydroxy-alkyl-furanone and hydroxy-alkyl-cyclopentenone) have been considered as major “building blocks” of humic substances and melanoidins.Aromaticities calculated from NMR spectral data of SM (“sugar” enriched melanoidins) and AAM (amino acid enriched melanoidins) coincide remarkably with the aromaticities of terrestrial and marine humics, respectively.     

CPMAS 13C NMR spectra of estuarine sedimentary humic acids

CPMAS ¹³C NMR spectra of two estuarine sedimentary humic acids were recorded on a Bruker WP-SY 200 spectrometer. Both samples were found to contain similar aromatic and aliphatic carbon fractions. The sedimentary humic acids have unusually high methoxyl contents and more than one type of methoxyl is indicated. The high methoxyl content may be related to relatively low values for estuarine sedimentary humic acid-metal complexes. Carbohydrate contents of the humic acid samples were also found to be low.     

13C NMR measurements of the genetic potentials of oil shales

Cross polarization, magic-angle spinning ¹³C NMR measurements have been made on raw oil shales that represent a variety of geologic ages, origins, depositional environments and source locations. A high degree of correlation was established between the fraction of aliphatic carbon measured by ¹³C NMR, and the genetic potential, calculated from Fischer assay data. The correlation is independent of the type of kerogen in the raw shale, and its degree of evolution. A short discussion on the validity of various correlations between physical/chemical properties of oil shales and Fischer assay oil yields is given.     

Cross polarization, magic-angle spinning C nuclear magnetic resonance spectroscopy of soil humic fractions

Cross polarization, magic-angle spinning ¹³C nuclear magnetic resonance spectroscopy was used to characterize humic fractions isolated from different soils. The acid fractions are more aromatic than the humin fractions, probably due to the higher polyssaccharide content of humins. However, fulvic acid fractions are more aromatic than the corresponding humic acid and humin fractions. These results can be interpreted in terms of the isolation procedure, because the high affinity of Polyclar AT for phenols results in higher aromaticities as compared with other isolation methods (e.g. charcoal).     

中国北方两种现代草地动物牙齿珐琅质δ^13C值与植被类型的关系初探

在简单了解研究区的植被、气候状况的基础上，分析了内蒙古锡林郭勒和青海海北两种典型草地食草动物牙齿的δ^13C值，测定了采样点表土有机质的δ^13C值。锡林郭勒的表土有机质碳同位素组成略分散，义与植被和微环境密切相关。海北的表层土壤有机质碳同位素组成比较集中。两地的碳同位素组成都偏轻，是植被中以植物含量少的反映。两地放牧动物的珐琅质δ^13C值分别比当地植物偏重12．9‰和13．5‰，或14．1‰和14．7‰。火灾等高温过程对动物牙齿的碳同位素组成可能没有显影响。     

[1H] and [13C]NMR studies on the importance of aromatic structures in fulvic and humic acids

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.     

Carbon content and carbonate 13C abundances in the Early Precambrian Swaziland sediments of South Africa

Carbon content (0.02–0.68% organic), carbonate content (0–69.7%) and carbonate ¹³C abundances (${}^{\mathrm{?}}\text{7.5?+2.3‰}$) were obtained on samples from the Swaziland sediments of South Africa, which are among the oldest known sedimentary rocks on earth (> 3·10⁹ years old). The carbon chemistry of these sediments may serve as evidence for early life and/or for products of chemical evolution. The variation of organic and carbonate carbon concentrations in different sedimentary horizons seems to be controlled by differences in depositional and diagenetic histories. The carbonate δ ¹³C values did not vary significantly from the ordinary range of Phanerozoic limestone values.     

The structure of freshwater humic substances as revealed by 13C-NMR spectroscopy

Freshwater humic substances from Lake Celyn, Gwynedd, N. Wales have been investigated by ¹³C-NMR spectroscopy. Carboxyl, aromatic, o-alkyl and alkyl resonances can be recognised. Varying pulse delay from 0.43 s to 2.5 sec has little effect on the magnitude of the signal ascribed to aromatic carbon, but there is a small nuclear Overhauser effect (1.45 at a pulse delay of 0.8 sec).The results show-that 24% of the Lake Celyn humic acid carbon is carboxyl and 40% is aromatic. The high proportion of aromatic carbon suggests the Lake Celyn humic acid is largely formed from terrestrial humic substances from the surrounding peaty watershed.     

孢粉浓缩物在AMS 14C测年研究中的应用及展望

可靠的¹⁴C测年材料是建立高精度年代序列的前提。在陆生植物残体缺乏的沉积类型中或某一沉积层位,利用其他¹⁴C测年材料可能会影响测年结果的精度。而陆生植物孢粉广泛存在于各类地质载体中,利用其浓缩物定年是解决这一问题的途径之一。文章综述了不同沉积类型孢粉浓缩物的提取方法及其测年结果的验证;成功提取了秦岭太白山高山湖泊大爷海表层沉积物中的孢粉浓缩物,其AMS ¹⁴C定年结果与全有机质年代对比表明高山封闭湖泊孢粉浓缩物能够提供较为可靠的年代估计且在一定程度上能避免碳库效应的影响;但仍需对湖泊岩芯多个层位开展多种测年材料（如陆生植物残体、炭屑、有机质）的对比定年研究以做进一步验证。基于前人及本研究提取经验,归纳总结出适用于湖泊沉积、泥炭沉积、黄土-古土壤序列以及冰楔冰中孢粉浓缩物的提取流程,主要分为前期的孢粉富集（酸碱法）和后期的纯化处理（化学法、镜下挑选与重液浮选）,并梳理了目前孢粉浓缩物在定年应用中需要注意的问题。探索沉积物孢粉浓缩物提取的新方法、改进并简化其现有提取流程、提高孢粉浓缩物提取效率（短时间内获取足量的、高含量的陆生植物孢粉）,将极大地促进孢粉浓缩物定年方法在晚第四纪年代研究中的应用。

     

Climate versus changes in 13C content of the organic component of lake sediments during the Late Quarternary

Several factors influence the long-term ¹³C record of the organic component in lake sediments. Two of the more predominant ones are changes in hardness of the water and changes in organic productivity. In general, during colder climatic episodes, ¹³C values are lower. Of 12 lakes studied, 4 have ¹³C records with large changes in ¹³C content that are to a certain degree correlative with climatic changes.     

Exploitation of relaxation in cross-polarization nuclear magnetic resonance spectroscopy of fossil fuels

The judicious choice of dipolar dephasing times or carbon magnetization holding times has been shown to improve resolution in solid state nuclear magnetic resonance (NMR) spectra of complex materials. Signals from protonated and alkylated aromatic carbons are reduced to enhance resolution of aromatic oxygenated groups. Rapidly rotating methyl groups can be resolved from other aliphatic carbon types. These techniques were used to investigate the structure of a brown coal, xylite fractions of a brown coal, a bituminous coal, an oil shale and a solvent-refined coal. The results allow estimates of the fraction of aromatic carbon that is protonated in coal to be made, and demonstrate that methyl groups in coal rotate rapidly at room temperature.     

河北省唐山地区丰台—野鸡坨断裂第四纪活动性——来自14C和磁性地层年代学的证据

丰台—野鸡坨断裂为唐山地区主要断裂之一，西侧为鸦鸿桥凹陷，东侧为唐山凸起，断裂两侧第四系厚度之差巨大。本文依据该断层两侧钻孔对其第四纪以来活动性进行初步的探讨。通过对丰台—野鸡坨断裂上下两盘PZK14和PZK20孔磁性地层学研究，并结合钻孔岩石地层，及浅部光释光和¹⁴C测年结果，建立第四纪地层格架。结果表明：两孔底部“泥包砾”为新近纪沉积；PZK14孔下更新统底界埋深为387 m，中更新统底界埋深为114 m，上更新统底界埋深为71 m，全新统底界埋深为6 m；PZK20孔下更新统底界埋深为155 m，中更新统底界埋深为73 m，上更新统底界为36 m，无全新世地层。丰台—野鸡坨断裂活动在早更新世时表现为逐渐增强的特点，活动速率由早期的5.4 cm/ka增加到13.9 cm/ka。中更新世断裂活动基本处于停滞状态，活动速率为1.0 cm/ka。晚更新世以后，断裂重新活动，且更加剧烈，活动速率达到了54.5 cm/ka。     

13C/12C ratio double cyclicity in a Miocene browncoal: isotopic signals and orbital forcing

A detailed stable carbon isotopic profile of a late Miocene browncoal seam from the Lower Rhine Embayment, Germany, reveals two clear separate cycles of different frequency: this is the first instance of this type of isotopic signature being recognized within coals. The ratio of the two frequencies suggests this isotopic signal possibly resulted from climatic or vegetational responses to orbital forcing. The cyclicity has been enhanced by the application of conventional filtering methods on the data set. An analysis of the seam's palynology indicates a correlation between heavier isotopic compositions and the presence of Sequoiapollenites polyformosus , whose parent plant is believed to have favoured moist climates and higher groundwater tables.     

河北沧州地区第四纪地下水36Cl示踪

通过对华北平原沧州地区第四纪地下水中宇宙成因核素36CI进行的测定,其浅层咸水的36Cl/Cl值为57×10-15,证实了该区浅层地下水的盐化成因主要是蒸发浓缩所造成.该区深层地下水中大气成因的36Cl所占的份额为33%～30%,系由上覆咸水下移所致.     

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state C nuclear magnetic resonance spectroscopy

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, CH_n 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.