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.     

Investigation of marine and terrestrial humic substances by H and C, nuclear magnetic resonance and infrared spectroscopy

Humic acids were isolated from 5 sediments in which the origin nature of the organic matter are both typical and different. The humic acids were characterized on the basis of elemental compositions, infrared spectra and ¹H and ¹³C NMR. This last technique, especially ¹³C NMR, provides qualitative and semi-quantitative information regarding aromatic structure. Combined data from the three techniques permits differentiation of marine and terrestrial organic matter as well as identification of mixtures of humic acids from the two sources.     

N-CPMAS nuclear magnetic resonance spectroscopy and biological stability of soil organic nitrogen in whole soil and particle-size fractions

Soil organic nitrogen was quantified by solid-state ¹⁵N cross-polarization nuclear magnetic resonance spectroscopy (NMR) during a 14-month laboratory incubation of a sandy loam soil amended with ¹⁵N-clover. In whole soil and particle-size fractions, the clover-derived N was always 85–90% amide, 5–10% guanidinium N of arginine, and 5% amino. Quantitativeness of these results was suggested by (1) analysis of a standard containing a complex mixture of organic ¹⁵N and (2) correlation of spectral intensities with ¹⁵N concentrations. Based on the unchanging proteinaceous NMR signature of clover-derived N throughout the incubation, differences in the mineralization/immobilization kinetics of clover-N among the different particle-size fractions appeared not to be linked to organic functional group. Kinetic analysis of the mineralization of ¹⁵N, with correction of rate constants for field temperatures, suggested that the proteinanceous ¹⁵N in the clay and fine silt fractions observed here had a mean residence time of 7 years in the field.     

Nuclear magnetic resonance spectroscopy of soils and related materials. Relaxation of 13C nuclei in cross polarization nuclear magnetic resonance experiments

Relaxation of ¹³C nuclei in a peat, a soil, and three soil fractions have been investigated in order to improve structural resolution and to investigate quantification of various carbon types. Rotating frame spin lattice relaxation times (T_1?'s) and transverse relaxation times (T₂′'s) are similar to those observed for coals. T₂′'s of carbons in different magnetic environments differ sufficiently that spectra can be obtained containing only nonprotonated carbon and methyl substituents if a 40 μsec delay without decoupling is inserted into the pulse programme before data acquisition (dipolar dephasing). Provided quantitative data is obtained in simple cross polarization experiments and allowance is made for loss in signal intensity of nonprotonated carbon during dipolar dephasing, then the fraction of aromatic carbon which is protonated in the samples can be determined.     

Analysis of the structure of dissolved marine humic substances and their phytoplanktonic precursors by H and C nuclear magnetic resonance

The structure of dissolved marine humic material and the intracellular and extracellular material from the diatom Phacodactylum tricornutum has been investigated by ¹H- and ¹³C-NMR spectroscopy. The results show that carbohydrates, highly-branched alkyl chains and to a lesser extent aromatic materials are important contributors to the structure of marine humic substances and aqueous extracts of P. tricornutum. There is a close relationship between the chemical structure of P. tricornutum exudate and dissolved marine humic material.     

固化盐渍土核磁共振微观特征

采用核磁共振技术,对不同配比的水玻璃、石灰+粉煤灰及石灰+粉煤灰+水玻璃的固化盐渍土的微观特征进行检测,结合无侧限抗压强度试验,分析了各固化方案的盐渍土固化效果,讨论了强度成因的微观特征机制。结果表明,不同固化土的孔隙特征有较大差异。石灰+粉煤灰固化盐渍土大孔隙减少;石灰+粉煤灰+水玻璃固化盐渍土孔隙总体积减少,但同时有大孔隙生成;水玻璃固化盐渍土孔隙总体增多,但随水玻璃浓度增大,孔隙体积有所减小。石灰+粉煤灰+水玻璃固化盐渍土抗压强度远大于其他固化方案,但是其孔隙结构并不是最优,说明颗粒间的胶结情况对固化效果的影响远大于孔隙特征。     

Use of ultrasonic treatment for extraction of humic acid with inorganic reagents from soil

The use of ultrasonic vibrations (1 hr) on the extraction of humic acids (HA) from a brown soil has been compared with the extraction by mechanical stirring (24 hr) with two extractants: 0.5 N and 0.1 M Na₄P₂O₇, followed by extraction with 0.5 N NaOH. In the pyrophosphate extraction, ultrasonic and mechanical treatments produced the same yield of HA. Further extraction with NaOH and mechanical stirring gave higher yields.The elemental composition of HA changed remarkably with both ultrasonic and mechanical systems. The HA extracted with ultrasonic treatment showed a higher ash content and a lower content of COOH and phenolic OH groups. These HA's showed higher optical density at 260 and 450 nm when pyrophosphate-extracted, and lower optical density when NaOH-extracted. Moreover the ultrasonic-treated HA in both extractants showed a lower E₄₀₀/E₆₀₀ ratio.Infrared examination confirmed the difference in chemical characteristics of extracted HA. The HA distribution in the different classes of nominal molecular weights by Sephadex gel filtration was influenced by both ultrasonic and mechanical systems, specially for molecular weights between 5000 and 150,000. It has been noted that the differences due to both systems are less marked than those caused by ssing different extractants.     

Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

砂岩铀矿成矿过程中有机质作用的实验研究--以吐鲁番-哈密盆地十红滩铀矿床为例

本文利用采自吐鲁番-哈密盆地西南部的样品,有针对性地做了一系列有机质抽提及分离实验,即①利用氯仿抽提岩石中有机质实验;②利用CS2-NmP(二硫化碳-N-甲基-2吡咯烷酮)抽提岩石中有机质实验;③腐殖质提取及分离实验。以上有机质抽提物及分离物分别做铀含量测试。通过实验发现,按以上实验顺序．岩石有机质提取物或分离物中铀含量依次有不同程度的提高,其中以腐殖质中分离出的黄腐酸(Fulvic acids)中铀含量最高,说明在吐哈盆地西南部砂岩铀矿的形成过程中有机质(主要是腐殖质和沥青质)的吸附作用起到部分作用．起最主要作用的是黄腐酸,而且与铀酰离子是以络合(或螯合)形式进行迁移。通过实验和分析,作者认为腐殖质(Humic substances)的络合作用和吸附作用在铀的迁移过程中是紧密相联的,而不是互相孤立的两种作用。在铀的迁移和沉淀富集过程中,黄腐酸(Fulvic acids)和腐殖酸(Humic acids)分别起到不同作用。     

Solid-state (H and C) nuclear magnetic resonance spectroscopy of insoluble organic residue in the Murchison meteorite: a self-consistent quantitative analysis

Complementary, double- and single-resonance solid-state (¹H and ¹³C) nuclear magnetic resonance (NMR) experiments were performed on a solvent extracted and demineralized sample of Murchison meteorite organic macromolecule. These NMR data provide a consistent picture of a complex organic solid composed of a wide range of organic (aromatic and aliphatic) functional groups, including numerous oxygen-containing functional groups. The fraction of aromatic carbon within the Murchison organic residue (constrained by three independent experiments) lies between 0.61 and 0.66. The close similarity in cross-polarized and single-pulse spectra suggests that both methods detect the same distribution of carbon. With the exception of interstellar diamond (readily detected in slow magic angle spinning single-pulse NMR experiments), there is no evidence in the solid-state NMR data for a significant abundance of large laterally condensed aromatic molecules in the Murchison organic insoluble residue. Given the most optimistic estimation, such carbon would not exceed 10% and more likely is a fraction of this maximum estimate. The fraction of aromatic carbon directly bonded to hydrogen is low (∼30%), indicating that the aromatic molecules in the Murchison organic residue are highly substituted. The bulk hydrogen content, H/C, derived from NMR data, ranges from a low of 0.53 ± 0.06 and a high of 0.63 ± 0.06. The hydrogen content (H/C) determined via elemental analysis is 0.53. The range of oxygen-containing organic functionality in the Murchison is substantial. Depending on whether various oxygen-containing organic functional groups exist as free acids and hydroxyls or are linked as esters and ethers results in a wide range in O/C (0.22 to 0.37). The lowest values are more consistent with elemental analyses, requiring that oxygen-containing functional groups in the Murchison macromolecule are highly linked. The combined ¹H and ¹³C NMR data reveal a high proportion of methine carbon, which requires that carbon chains within the Murchison organic macromolecule are highly branched.     

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.     

Analyses of insoluble residues of altered organic matter by C CP/MAS nuclear magnetic resonance

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.     

缩短核磁共振测定冻土未冻水含量实验时间的方法

为利用核磁共振(NMR)技术更快地测试得到冻土中未冻水的含量, 首先对传统的单试样测试方法进行了分析, 探究了其实验时间过长的原因. 然后, 基于传热学中的集总参数法, 研究了小体积试样在空气中以自然对流传热为冷却方式的温度变化特征. 根据试样温度与时间的对应关系, 提出了多试样连续测试法. 最后, 以一种黏土为例, 分别利用多试样连续测试法和单试样测试法测量了土样冻结过程中NMR信号强度随温度变化的关系. 实验结果表明: 二者的测量结果非常接近, 但连续测试法耗费的时间非常少. 综合比较两种利用NMR技术所耗费的时间和实验结果的精确程度, 多试样连续测试法是可行的.     

基于核磁共振技术的淤泥固化水分转化机制研究

为了揭示淤泥固化体的微细观水分分布与工程特性的内在联系,针对水泥固化湖泊淤泥,基于柔性壁渗透、无侧限抗压及核磁共振（NMR）试验,探明淤泥固化过程中的水分转化和孔隙结构演化机制,并与固化体的渗透系数k、无侧限抗压强度 和变形模量 建立关联。试验结果表明：7 d龄期内水化反应速率快,淤泥固化体内的大量孔隙水转化成水化物中的化合水,最可几孔径减小,形成孔隙结构骨架主体,导致k值降低、 和 增大;7 d后,只有当孔隙水扩散穿透水化物膜层,水化反应才继续缓慢进行,但 和 仍大幅增长;化合水量 与lgk存在线性关系,而 - 和 - 均呈指数关系。基于微观水分参数与工程特性的量化关系模型,可充分揭示水泥固化淤泥的宏微观演化机制。     

The decomposition of windrowed, chipped logging slash and tree seedling response: A plant growth and nuclear magnetic resonance spectroscopy study

Forest management practices historically have reduced the mass of logging slash to facilitate planting and reduce fire risk. However, coarse woody debris (CWD) is considered an important component of unmanaged forests of western and coastal North America. An experiment was established in northern California using chipped logging slash concentrated in windrows to emulate large fallen logs to determine the effects of alternative logging residue treatments on soil fertility and the performance of planted ponderosa pine. Chip piles warmed faster than mineral soil, but upper regions dried quickly during the dry summers. Fourteen years after planting, growth response was positive, as seedling volume declined with distance from the windrows. After 6 and 10 years, chip samples showed little variation in total C, but total N was higher for 10-year samples, with slightly higher values at the base and for N-fertilized sections. Analysis by solid state ¹³C CPMAS NMR, verified by spin-counting and triplicate analysis showed only subtle differences among 10-year samples, with non-carbohydrate C slightly more abundant at the base of the piles and for windrows originally fertilized with N. However, proton spin relaxation editing (PSRE), based on differences in T_1H relaxation rates, was able to distinguish between C in relatively undecomposed lignocellulose (slowly relaxing) and more decomposed material and microbial residues (rapidly relaxing). The small differences between top and base, and between fertilized and control samples were concentrated in the rapidly relaxing component. Bulk composition of 10-year chip windrows was similar to CWD naturally decomposed by white-rot fungi, but PSRE offers a new approach to monitor spatially heterogeneous development of microsites more characteristic of brown rot.     

离子浓度对冻土核磁共振响应信号的影响分析及研究

离子浓度在一定程度上会引起冻土冻融过程中其未冻水的含量变化,进而影响冻土的核磁共振响应.为了研究冻土冻融过程中离子浓度对其核磁共振响应的影响规律,笔者采用的试验样本是将不同浓度的NaCl溶液与马兰黄土混合,配制成NaCl含量不同、初始含水量相同的各样本,研究其弛豫特性.通过分析不同温度点下各样本的核磁共振响应特征,得到不同离子浓度对冻土核磁共振响应的影响规律.结果表明,核磁共振信号幅值随着离子浓度的增大而增大,但是横向弛豫时间T2不受离子浓度影响;在冻土冻融过程中,冻土中流体受温度和离子结晶物化作用的双重影响,样本的未冻水含量在不同温度区间的变化有所不同,但是在大于5℃和低于-20℃区间内,未冻水含量趋于稳定.     

14C analysis of aliphatic hydrocarbon fractions from the hypersaline Lake Tyrrell,southeast Australia

Conventional biomarker studies typically interpret the distribution, structure and stable isotopic (e.g. ¹³C, D) composition of sedimentary hydrocarbons and polar compounds. However, compound and compound class specific ¹⁴C analysis (CSRA) is becoming increasingly relevant for characterising millennial scale residence and mobilisation of sedimentary organic carbon (OC). Here, the ¹⁴C content of the aliphatic and bulk fractions from shallow cores from the hypersaline playa, Lake Tyrrell, southeast Australia were compared. The aliphatic hydrocarbon fractions (predominantly n-alkanes) were substantially older than the corresponding bulk fractions, indicating the presence of active reservoirs of ancient carbon, likely derived from aeolian reworking of sediments. The ¹⁴C ages of the aliphatic hydrocarbons in the core revealed two noticeable shifts in age and source of ancient OC that were not apparent using biomarker composition and sedimentology alone. The study shows that aliphatic hydrocarbons are relatively simple to isolate, even from organically lean (ca. 0.05% TOC) terrestrial sediments, and their ¹⁴C ages yield information about carbon mobilisation and preservation not amenable to conventional analysis.     

Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state C nuclear magnetic resonance

Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studies by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing ¹³C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage.     

桂林毛村岩溶区不同土地利用方式土壤有机碳矿化及土壤碳结构比较

应用土壤培养法,比较分析了桂林毛村岩溶区不同土地利用方式(农田、灌丛和林地)土壤在25℃、黑暗条件下培养90d有机碳矿化速率的差异(以90d累计释放的CO2-C计)。农田土壤矿化释放的CO2-C含量分别比灌丛和林地少62.9%和56.6%。利用6mol/L的HCl酸解法得到惰性碳含量,并利用三库一级动力学方程在SAS8.2软件中通过非线性拟合得到三种土地利用方式的活性碳库、缓效性碳库的大小及其分解速率,计算得出各库驻留时间。结果表明各土地利用方式均为活性碳库含量最少,占总有机碳的比例在1.82%~2.71%之间,平均驻留时间在8.4~16.3d之间;缓效性碳库次之,占总有机碳的比例在33.91%~45.47%之间,平均驻留时间为4.8~7.7a之间;惰性碳库所占比例最大,在51.82%~64.01%之间,平均驻留时间为假定的1000a。通过固态13C交叉极化魔角自旋核磁共振(13CCPMASNMR)方法对土壤碳结构进行分析,结果表明:与灌丛和林地相比,受人类活动干扰较多的农田烷基C和芳香C的比例增加,烷氧C和羰基C的比例降低;烷基C/烷氧C和疏水C/亲水C的大小顺序均为农田>林地>灌丛,而脂族C/芳香C的大小顺序则相反,即灌丛>林地>农田。这说明农田土壤有机碳分解程度较高,难分解程度增加,难分解有机碳比例增加。      

^29Si,^27Al Magic—Angle—Spinning Nuclear Magnetic Resonance（MAS NMR） Studies of Kaolinite and Its Thermal Transformation Products

²⁷Al,²⁹Si MAS NMR studies of kaolinite and its thermal transformation products show that in the kaolinite-mullite reaction series there is an extensive segregation of Al₂O₃ and SiO₂ and the reaction of Al₂O₃ with SiO₂ to form mullite is the main path of mullite formation. At about 850° C, the peak intensity of A1(V) reaches its maximum and with the further rise of temperature the A1(V) signal completely disappears. At about 950°C, γ-Al₂O₃ accounts for about 71% of the material phases containing Al atoms. In the series there is no obvious presence of Al-Si spinel. The²⁷Al and²⁹Si MAS NMR spectra show that there is an obvious difference between the temperature points for Al-O₂(OH)₄ octahedral sheet collapsing and Si-O₄ tetrahedral sheet breaking down.