核磁共振测深方法在多年冻土区找水中的应用

通过核磁共振测深( MRS)方法在多年冻土区找水实例的分析、解释,并结合钻孔资料的综合研究,对在多年冻土区利用MRS方法探测地下含水层埋深、厚度及地下水涌水量的计算进行了详细的解析,并取得了良好的应用效果。阐明了该方法在多年冻土区找水具有含水信号反映明显、信噪比高和具唯一性解析结果等的独特技术优势,也指出了该方法在判断含水层岩性、涌水量计算等方面存在的不足,揭示了MRS方法在多年冻土区寻找地下水的良好应用前景,为在多年冻土区寻找地下水提供了一定的借鉴经验。     

冻土未冻水含量的低场核磁共振试验研究

采用低场核磁共振技术测试了冻融循环过程中不同土质、不同NaCl离子浓度饱和试样的未冻水含量,结合T2分布曲线从微细观角度分析了冻融过程中未冻水在孔隙赋存分布情况。试验结果表明：冻结过程可分为过冷度段、快速下降段、稳定段3个阶段,而融化过程仅存在稳定段、快速融化段,并不存在与过冷现象对应的过热现象。冻结时大孔隙的水首先冻结,而融化时孔隙水的增加却是从小孔隙开始的,这是由水分热动力学势能的差异导致孔隙水冻结和融化在时间上的有序性。并且分析了冻融循环中土质类型、离子浓度对未冻水含量的影响,以及探讨了冻融过程出现的滞后现象的原因。     

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。     

Analysis of fluid inclusions using nuclear magnetic resonance

Nuclear magnetic resonance (NMR) spectra from ²³Na and ³⁵C1 in fluid inclusions in samples of quartz and beryl show the potential of NMR as a powerful analytical technique for the study of fluid inclusions.     

Orientation and motion of water molecules in cordierite: A proton nuclear magnetic resonance study

Conventional and solid state proton nuclear magnetic resonance (NMR) techniques have been used to examine water molecules in the channels of a single crystal of cordierite, (Mg, Fe)₂Al₄Si₅O₁₈, as a function of temperature, magnetic field, and orientation. Only one type of water was found rather than water in two distinct rigid orientations which were indicated by earlier infrared spectral studies. However, the measured dipolar splittings indicate that this water is in rapid motion. Shifts in the dipolar doublet due to Fe²⁺ impurities indicate that the water molecules are not moving among adjacent channel sites along a channel cavity. A two-site hopping model is proposed involving the major residence time spent with the hydrogen-hydrogen vector parallel to the channels, a minor residence time spent with the hydrogen-hydrogen vector perpendicular to the channels, and a short time (<1 μs) in transit. This model fits both the present NMR data and previously reported infrared absorption data and is compared to previously reported neutron diffraction data.     

地面核磁共振技术在隐伏火烧区富水性探测中的应用

煤层隐伏火烧区上覆基岩复合含水层(包括风化基岩和烧变岩含水层)是煤层开采的主要威胁之一, 明确隐伏火烧区的富水性对矿井水害防治具有重要意义。基于此, 以发生过较大突水事故的柠条塔煤矿为研究对象, 利用地面核磁共振(SNMR)技术开展隐伏火烧区含水层富水性探测并对其进行分析和验证。结果表明, 隐伏火烧区共有2个含水层位, 分别为第四系松散砂层含水层和1-2 上煤上覆基岩含水层; 第四系砂层含水层富水性受地表地形及其下隔水层顶部起伏形态影响水平变化较大; 1-2 上煤上覆基岩含水层富水性总体西南较低、北东较高, 该含水层厚度9~30 m, 局部相对较厚, 推测为1-2 上煤火烧区风化基岩和烧变岩含水层的叠加反映; 研究区内1-2 上煤上覆基岩含水层总体呈现出西部及中部偏东南区域富水性相对较大, 其余区域富水性相对较小。利用SNMR得到的含水层富水程度与探放水孔及水文孔的涌水量结果大致相同, 表明该方法的勘探结果相对可靠, 可用于隐伏火烧区富水性的探测。      

Analysis of the organic matter of oil shales by nuclear magnetic resonance

¹³C NMR spectroscopy was applied in the investigation of the structure of the organic matter in oil shales. By using Proton Enhanced Nuclear Induction Spectroscopy, a fair resolution of aliphatic and aromatic carbon signals was achieved. This method provided information on the relative ratio of aliphatic and aromatic carbons within a given set of samples (Aleksinac, Kimmeridge, Colorado, Australian torbanite and Estonian kukersite).     

Comparison of oil shales and kerogen concentrates by C 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.     

Unfrozen water as a function of clay microstructure

A previous study of microstructural changes in freezing clay suggested that a “dispersed” freshwater clay should have a higher percentage of unfrozen water than a (leached) marine clay with similar mineralogical and granulometrical compositions. This report describes an investigation where two such clays were actually compared concerning their contents of unfrozen water. The results confirmed the hypothesis. Thus, the influence of clay microstructure on the amount of unfrozen water was clearly shown. The degree of particle aggregation and the density of the particle aggregates are the main microstructural parameters.     

利用核磁共振勘测滑坡的水文地质条件

滑坡水文地质条件是最易变、最难确定的,对滑坡的稳定性影响也很大。利用核磁共振(NMR)技术,可以分析确定滑坡各层岩土体的含水量、孔隙度、渗透率、渗透系数等水文地质参数。根据含水量的变化,可以确定滑体的结构特征、滑面位置、地下水的分布,为建立符合实际的滑坡模型及滑坡稳定性分析评价提供依据。介绍了利用NMR技术来查明滑坡水文地质条件的原理和方法及其在赵树岭滑坡工程中的成功应用情况。     

核磁共振与水文地质钻探联合技术确定盐湖晶间卤水层富水性

中国西部大型干旱盆地盐湖中,承压卤水含水层因其中所赋存的固--液相钾矿资源储量大而成为主要含矿层。采用地面核磁共振与水文地质钻探相结合的技术方法对柴达木盆地某盐湖进行的承压卤水可采性试验,获取了含水层的相关物理参数,并将其解译为相关的水文地质参数。通过水文地质综合判断,确定了含水率 5. 4% 的富水地段。水文地质钻探验证获取了稳定丰富的涌水量,并使之成为采卤量 1. 5 ×104m3/d、KCl 含量 1. 67% 的工业性开采水源地。结果表明,核磁共振与水文地质钻探联合技术是确定盐湖晶间卤水层富水性的可靠右有效的方法。     

Chemical structural studies of natural lignin by dipolar dephasing solid-state 13C nuclear magnetic resonance

Two natural lignins, one from a gymnosperm wood the other from angiosperm wood, were examined by conventional solid-state and dipolar dephasing ¹³C nuclear magnetic resonance (NMR) techniques. The results obtained from both techniques show that the structure of natural lignins is consistent with models of softwood and hardwood lignin. The dipolar dephasing NMR data provide a measure of the degree of substitution on aromatic rings which is consistent with the models.     

Volatiles from Hawaiian submarine basalts determined by dynamic high temperature mass spectrometry

Quantitative measurements of volatiles from Hawaiian submarine basalts have been made using a Knudsen cell dynamic-mass spectrometer system. The principal advantage of the technique is the ability to determine simultaneously the absolute amounts of more than one volatile released from the same sample.From mass pyrograms it was observed that the release of water was bimodal, with the major release occurring above 600°C. Water released below this temperature is believed not to have been present in the magma at the time of extrusion. Sulfur dioxide was evolved only after the bulk of the water was released and coincided with the general expansion and melting of the sample. Sulfur and carbon- containing gases which were released in surges (above 1000°C) correspond to the bursting of bubbles from the softened basalt.The molar amounts of vesicle gases were plotted as a function of extrusion depth. A change in the slope of the resulting linear curve indicates saturation of the basalt with respect to water.     

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。     

核磁共振在滑坡研究中的应用技术

应用核磁共振找水仪测试成果,分析确定滑坡各层岩土体的含水量、孔隙度、渗透率、渗透系数.根据含水量的变化,确定滑坡结构特征、地下水分布及各层滑动带位置.与钻孔资料的对比分析表明,该技术的分析结果与钻孔数据吻合较好,可为建立符合实际的滑坡模型提供可靠依据.     

31P solid-state nuclear magnetic resonance spectroscopy of aluminum phosphate minerals

This study examines the links between ³¹P solidstate NMR studies of aluminum phosphate minerals and their crystallographic structures. We found that ³¹P isotropic chemical shift values, _iso, carry little information about mineral structures. There seems to be no relation between the chemical shift anisotropy, =₃₃–₁₁ (₃₃>₂₂> ₁₁), and indicies of phosphate-tetrahedra distortion. ³¹P¹H heteronuclear magnetic dipole interactions, on the other hand, carry important information about hydrous phosphate mineral structures, information that should prove to be quite valuable in studies of phosphate adsorbed on mineral surfaces. This interaction can be measured through a variety of qualitative and quantitative experiments. It appears that spin diffusion is so rapid that subtle differences in hydrogen-bonding environments cannot be resolved.     

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.     

Structural studies of imogolite and allophanes by aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopy

High-resolution aluminum-27 and silicon-29 nuclear magnetic resonance spectra of natural and synthetic imogolites and allophanes obtained using high-field“magic-angle” sample-spinning (MASS) techniques indicate that the imogolite and protoimogolite components of allophanes are characterized by sharp (≈3 ppm) silicon-29 resonances at ?78±1 ppm from tetramethylsilane (in accord with Barron et al. 1982), and quite narrow (≈10 ppm at 11.7 Tesla) aluminum-27 resonances, at 5.2±1 ppm from Al(H₂O) ₆ ³⁺ (in accord with Wilson et al. 1984). However, the spectra of natural allophanes usually contain significant intensity arising from a less well defined material, characterized by a broad (≈20 ppm) silicon-29 resonance centered at ?90±2 ppm from tetramethylsilane, and a second relatively narrow (≈15 ppm at 11.7 Tesla) aluminum-27 resonance at 58.5±2 ppm from Al(H₂O) ₆ ³⁺ . Similar characteristic spectral features are exhibited by a synthetic amorphous Si:Al (1:1) gel, and presumably indicate the presence of framework aluminosilicate materials in the gel, and in most allophanes.     

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.