Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

基于SVD和BRD的二维核磁共振测井正则化反演算法研究

二维核磁共振能从"弛豫-扩散"两个维度上展现流体性质,在识别稠油储层方面具有理论优势,是当前核磁共振测井技术的研究热点.本文深入研究二维核磁共振测井原理,系统分析CPMG-DE脉冲序列测量扩散系数与弛豫时间的方法,结合核磁共振二维谱数理模型,提出一种基于SVD和BRD的正则化反演算法.该算法通过SVD压缩数据,采用带非负约束的Tikhonov正则化方法求解流体"弛豫-扩散"分布,并基于BRD算法迭代确定最佳正则化因子.模拟实验与数值分析表明,该算法无需先验信息、运算效率高、相对误差小,在原始数据信噪比低至50时,仍可有效获取流体(T2,D)二维分布.在二维核磁共振测井数据实时解释应用中,该方法较传统反演算法(如TSVD)具有较大优势.同时,在自主研发的核磁共振测井仪测量CuSO4溶液(T2,D)分布的实验显示,本文设计算法对弛豫时间和扩散系数的反演误差分别仅为2%和4%,较TSVD算法有较大改善.     

基于核磁共振测井资料构建水谱库的流体性质识别方法

以海拉尔地区为例,提出了基于核磁共振T2谱构建水谱库进行流体性质识别的一种新方法,实测核磁谱包含了孔隙结构、水和油气的信息,构建的水谱来自于水层的核磁实测谱,相当于消除了油气的影响,其基本原理是应用构建的水谱库与实测谱的差异识别流体性质。通过在海拉尔地区应用,得到了较好的应用效果。     

Study of macroaggregate composition using FT-IR and H-NMR spectroscopy

Mucous macroaggregates, recently observed in the northern Adriatic in summer of 1997 and late spring of 2000, are primarily the product of phytoplankton (diatom) exudates during favourable environmental conditions in late spring, and can be viewed as macrogels. The FT-IR and ¹H-NMR spectra of macroaggregate samples from the northern Adriatic, collected in different formation stages in July 1997, August 1997, September 1997 and June 2000, as well as of cultured diatom Skeletonema costatum, showed that they are similar and composed of aliphatic components and polysaccharides bonded through carboxylic and amide groups, and organosilicon compounds. The stability of macrogels of macroaggregates is, according to FT-IR and X-ray analyses, most probably enhanced by interactions with entrapped particles of calcite, quartz and clay minerals. These organic-mineral associations seem to be important for mucous phenomena. According to ¹H-NMR spectra, the temporal differences in macroaggregate composition show a relative increasing percentage of organosilicon compounds and aliphatic components bonded to carbohydrates through ester and amide groups, and an increasing ratio between aliphatic structures and carbohydrates. This indicates that aliphatic chains bonded to Si and carbohydrates may contribute to the persistence and stability of macroaggregates in the summer stratified waters in the northern Adriatic, while the temporal decrease of carbohydrate content is most probably due to microbial and photochemical degradation of algal reserve polysaccharides.     

Dissolved Organic Carbon Fractions Formed during Composting of Municipal Solid Waste: Properties and Significance

The properties and transformation of dissolved organic matter (DOM) extracted (10 L water per kilogram compost) from municipal solid waste (MSW) compost at five stages (days 47, 77, 105, 126, and 187) of composting were investigated. The DOM was fractionated into hydrophobic or hydrophilic neutrals, acids, and bases. The unfractionated DOM, the hydrophobic acids and neutrals (HoA and HoN, respectively), and the hydrophilic neutrals (HiN) fractions were studied using solid-state ¹³C-NMR, FTIR, and DRIFT spectroscopy. The HoA fraction was found to be the dominant (percentage of total DOM) hydrophobic fraction, exhibiting a moderate increase during composting. The HoN fraction increased sharply from less than 1% to 18% of the total DOM during 187 days of composting, while the hydrophobic bases (HoB) exhibited the opposite trend. The HiN represented the major fraction of the hydrophiles up to 120 days of composting, decreasing thereafter by 38%. The relative concentration of the hydrophilic acids and bases (HiA and HiB, respectively) exhibited no consistent trend during composting. DRIFT spectra of the unfractionated DOM taken from the composting MSW revealed a decreasing level of polysaccharide structures with time. The ¹³C-NMR and FTIR spectra of the HoA fraction exhibited a polyphenol-humic structure, whereas the HoN spectra exhibited strong aliphatic features. The spectra of the HiN fraction confirmed its polysaccharide nature. During the final stage of composting, the DOM concentration was steady, while a relative decrease of HiN concomitant with an increase of HoA and HoN fractions was observed. These indicate that the DOM contained a low concentration of biodegradable organic matter and a higher content of macromolecules related to humic substances. The biological significance and heavy metal binding of these fractions are being studied based on earlier observations showing enhanced plant growth in the presence of DOM extracted from mature as opposed to immature compost.     

不饱和古罗糖醛酸三糖和甘露糖醛酸三糖的结构表征

以双功能褐藻胶裂解酶 (Pseudoalteromonas sp.strain No. 2 72 )分别降解均聚古罗糖醛酸(PG)和均聚甘露糖醛酸 (PM) ,经 Bio- Gel- P6和 POROS- HQ2 0分离得到 2种三糖纯品 ,经 ESI- MS,1 H- NMR,1 3 C- NMR,1 H- 1 H COSY,1 H- 1 3 C HMQC确定其结构为 Δ4,5-古罗糖醛酸 - α(1→ 4 ) - L-古罗糖醛酸 -α(1→ 4 ) - L -古罗糖醛酸 (简写为Δ GG)和Δ4,5-甘露糖醛酸 -β (1→ 4 ) - D-甘露糖醛酸 -β (1→ 4 ) - D-甘露糖醛酸 (ΔMM) ,为进一步从事构效关系研究提供结构信息。     

液氮冻结条件下岩石孔隙结构损伤试验研究

液氮温度极低,约在-195.56^-180.44℃之间,当与岩石接触时会对岩石孔隙结构产生损伤。根据这一特点,低温液氮有望作为压裂流体对储层进行压裂改造。为了研究液氮冻结对岩石孔隙结构损伤的影响,选取两种不同砂岩岩样,分别在不同初始含水饱和度条件下进行液氮冻结处理。对冻结前、后的岩样进行孔隙度以及核磁共振测试,得到岩样在冻结前、后的孔隙度、横向弛豫时间T2分布以及T2谱面积变化情况。试验结果表明:液氮冻结会对岩石的孔隙结构产生损伤,损伤程度受到岩性、孔隙度和岩石含水饱和度等因素影响;岩石含水饱和度越大,损伤就越严重,当岩石含水饱和度达到100%时,岩石表面产生了明显裂纹;岩石在液氮冻结下损伤形式主要是微孔隙的发育和扩展,微孔隙的增加会使岩石孔隙结构的连通性增强,甚至会产生新的大尺寸孔隙,从而对孔隙结构造成严重损伤。     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

多尺度孔隙岩石的核磁共振扩散耦合现象及其探测方法

油藏岩石的孔隙连通性是反映流体渗流难易程度的重要参数,对渗透率、有效孔隙度等岩石物理参数的评价具有重要作用.连通的孔隙中,核磁共振（NMR）弛豫的交换会产生扩散耦合现象,可作为孔隙连通性的表征和探测方法.本文提出利用横向弛豫T₂-T₂脉冲序列测量岩石的扩散耦合现象.运用随机游走方法模拟多孔岩石的核磁共振响应特征,分析扩散耦合的影响因素,推导表征扩散耦合强度的弛豫交换速率计算公式.结果表明：孔隙间的扩散耦合强度与T₂-T₂脉冲序列的混合时间呈正相关性,基于双孔弛豫交换模型推导的弛豫交换速率计算公式能够准确表征双尺度孔隙系统的扩散耦合强度.在孔隙尺寸不满足快扩散条件时,会出现与扩散耦合无关的非对角峰信号.针对含多类型孔隙的碳酸盐岩模型,随混合时间的增加,扩散耦合强度变大,一维T₂谱的形态畸变程度加重,在T₂-T₂二维谱中,代表微裂缝、粒间小孔、溶蚀大孔的信号能量变化趋势不同,反映不同类型孔隙间的连通性存在差异.本文的分析与讨论丰富了核磁共振弛豫在岩石物理性质评价中的应用方向,对利用核磁共振评价复杂孔隙岩石的孔隙结构和连通性提供了新思路和新方法.

     

核磁共振技术应用的新领域——探查地下水

利用核磁共振（ＮｕｃｌｅａｒＭａｇｎｅｔｉｃＲｅｓｏｎａｎｃｅ缩写为ＮＭＲ）技术探查地下水仅有二十多年的历史,文中简要介绍了ＮＭＲ找水方法的发展状况,原理和方法特点,重点介绍了中国地质大学（武汉）利用ＮＭＲ找水方法在中国一些地区找水取得的成效,最后指出了ＮＭＲ找水方法的发展趋势。