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.     

[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.     

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 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.     

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.     

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.     

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.     

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。     

Structural investigations of Australian coals II: A 13C-NMR study of the humic acids from Victorian brown coal lithotypes

The experimental conditions allowing quantitative interpretation of liquid state ¹³C-NMR spectra of the humic acids, derived from the five Victorian brown coal lithotypes are described. The structure of the two classes of humic acids investigated for each lithotype vary significantly in their level of aromaticity, the level of polar functional groups and aliphatic chains attached to their polyaromatic skeletons. Variation is also observed in the degree of aromaticity and oxygen-containing functions of humic acids with lithotype. These data are interpreted in the light of paleobotanical evidence, which suggests that the lithotypes represent variations in depositional environment and input to the coal seam.     

加速器质谱~(14)C制样真空系统及石墨制备方法研究

~(14)C制样真空系统和石墨制备方法是高精度低本底~(14)C加速器质谱(AMS)测量的关键,而碳污染、石墨产率不稳定和同位素分馏等问题是限制该技术发展的主要难题。为了降低传统在线还原法对制样系统长时间静态真空的要求和解决Zn-TiH_2/Fe火焰封管法中不可控的CH_4等问题,提高石墨合成的稳定性和控制本底,本文建立了基于Zn/Fe火焰封管法的~(14)C制样真空系统和石墨制备方法。通过比较Zn/Fe在线法和Zn/Fe火焰封管法对石墨束流性能以及标样的影响,发现Zn/Fe火焰封管法相较Zn/Fe在线法能明显克服大气泄漏问题,改善化学流程本底(0.24～0.32pMC),提高方法测年上限(47000～48000ya),同时石墨束流输出稳定。进一步利用标准样品和本底样品评估了Zn/Fe火焰封管法的技术特点,实验结果表明该法的精密度好(RSD=0.35%,n=20,标样OXⅡ),准确度高(IAEA系列标样的测定值与认定值线性拟合方程y=0.9969x+0.0013,R~2=1),实验本底低(无机碳46296±271ya和有机碳48341±356ya)。因此,该石墨样品制备真空系统及Zn/Fe火焰封管法技术具有石墨品质优、化学流程本底低、准确度和精密度高等特点,满足高精度低本底~(14)C-AMS测定石墨样品制备要求。     

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.     

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.     

用树轮δ13C重建1685年以来的大气CO2浓度变化趋势

对采自浙江西天目山地区的3株柳杉树盘,交叉定年后,测定了3株树轮^δ13C的年序列,分析了3株树轮^δ13C序列中所含的共同环境变化信息。用二项式拟合法去除气候因素引起的3个^δ13C序列的高频变化,得到3个低频变化序列。分析了theLowDome冰芯记录的大气CO₂浓度与树轮^δ13C序列低频变化趋势的关系,建立了相应的转移函数,重建了天目山地区1685年以来大气CO₂浓度变化。结果表明:用3株树轮^δ13C序列重建的结果有较好的一致性,并与南极冰芯的记录及前人研究结果有很好的吻合。这一结果表明用同一地区不同树木个体的树轮^δ13C序列的低频变化序列可以重建出基本一致的大气CO₂浓度变化历史。     

Structural investigations of Australian coals—III. A 13C-NMR study on the effects of variation in rank on coal humic acids

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.     

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。

     

高岭石热转变产物^29Si、^27Al魔角旋转核磁共振研究

运用魔角旋转核磁共振结合红外光谱及X射线衍射等手段，研究了苏州高岭石的560－1600℃热转变产物，主要获得以下结论：（1）高岭石－偏高岭石－莫来石的转变系列的确存在结构上的连续性。其转变经历了几个阶段；脱羟阶段（400－600℃），偏高岭石阶段（600－800℃），相分离阶段（800－1100℃），莫来石阶段（1100－1600℃）。（2）莫来石形成过程没有出现Al2O3的大量分凝，但存在SiO2的分凝。（3）偏高岭石－莫来石转变过程的中间相为Al-Si尖晶石和准莫来石。（4）引起1000℃放热反应的主要因素是准莫来石的形成。     

1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

¹H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH₂)_n - CH₃ (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.     

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.