硅藻土中水的NMR研究

本文用ＮＭＲ技术研究硅藻土中水的存在状态和特征及灼烧条件下的脱水和室温大气下的重吸水过程。样品包括一个宝石级单矿物蛋白石和采自雷州半岛地区的海康卜昌和徐闻九亩的硅藻土地表样和它们经不同温度自理后的产物。     

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。     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

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.     

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.     

应用核磁共振成像(NMRI)技术研究复合剂驱油特征

本文应用核磁共振成像技术,在均值、非均值模型中研究了复合剂驱油动态实验过程。观察及分析了复合剂驱油特征和效果,对复合剂驱油段塞前缘进行了实时跟踪,得到了复合剂驱油段塞前缘油墙的形成及剩余油分布与运移的二维图像,给出了复合剂驱油后,剩余油的饱和度分布曲线。实验表明:在层状非均值地层中,若渗透率差异大,复合剂段塞主要进入高渗层,而波及不到低渗层,即复合剂波及效率低。若渗透率差异小,复合剂段塞大部分进入高渗层,有少部分进入低渗层,即复合剂波及效率较高。     

GC-MS联合二维核磁对文蛤多糖Fr.2A组分结构的解析

采用GC-MS联合二维核磁的方法,对文蛤均多糖结构进行解析。运用双酶辅助水提的方法,提取文蛤粗多糖(MMPX),分离纯化得到文蛤均多糖,并通过气质联用技术(GC-MS)和核磁共振波谱(1D,2D NMR),对文蛤均多糖的结构进行了分析。结果表明,从文蛤中提取得到文蛤粗多糖(MMPX),经分离纯化得到高纯度文蛤均多糖Fr.2A,其单糖组成为葡萄糖(Glc)。GC-MS分析发现,Fr.2A存在三种残基单元1,4-Glcp、T-Glcp和1,4,6-Glcp,摩尔比为5.58︰1.26︰1.0;核磁共振波谱分析表明,Fr.2A是以α-(1→4)与少量α-(1→6)连接为主链,并存在少量的α-(1→6)和β-(1→4)支链的新型水溶性D型吡喃葡聚糖。     

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.     

Chemical and spectroscopic characterization of dissolved humic substances in a mangrove-fringed estuary in the eastern coast of Hainan Island, China

Mangrove-derived dissolved organic matter(DOM) has an important effect on estuarine and coastal area on a large scale.In order to improve the understanding of origin,composition,and fate of DOM in mangrove-fringed estuarine and coastal areas,dissolved humic substances(DHS) were isolated from one mangrove pore-water sample and one near-shore seawater sample downstream the mangrove pore-water site in the eastern coast of Hainan Island,South China.Fulvic acids,humic acids and XAD-4 fractions were obtained from the two water samples by using a two-column array of XAD-8 and XAD-4 resins.Chemical and spectroscopic methods were used to analyze the features of these DHS.Compared to the mangrove pore-water DHS,the near-shore seawater DHS were found rich in 13 C with lower C/N ratios and more aliphatic compounds and carbohydrates,but less aromatic structures and carboxyl groups.As for the three fractions of the two DHS,XAD-4 fractions contain more aliphatics,carbohydrates,carboxyl groups,and enrich in 13 C with respect to both fulvic and humic acids.Photo-oxidation transformation and contribution from marine-derived DOM were considered as the main reasons resulted in the difference in compositional features for these DHS in this study.