巴西绿欧泊的宝石学特征

近期国内珠宝市场上出现一种产自巴西的绿欧泊,该类绿欧泊表现出的宝石矿物学特征与传统的欧泊有着明显差异。采用常规宝石学测试手段,并结合电子探针、X射线粉末衍射、扫描电子显微镜、红外吸收光谱、紫外吸收光谱等测试分析方法,就其化学成分、物相、微结构、谱学特征及颜色成因等问题展开初步研究。结果表明,巴西绿欧泊的主要矿物组成为蛋白石,含不等量的α-方石英和α-鳞石英等次要矿物,整体呈不规则胶柬状结构,局部微波纹理发育;该类欧泊主要由直径约10～30nm的SiO2球粒聚集而成;由H2O和M—OH倍频振动致近红外吸收谱带位于7000cm-1处,由H2O合频振动致近红外吸收谱带分别位于5200,5612cm叫处,由M—OH与[SiO4]合频振动致近红外吸收谱带位于4600-4100cm-1范围内。笔者还对巴西绿欧泊的呈色机理一并给予了探讨。     

电气石中水的振动谱学研究及其意义

利用偏振喇曼光谱（ＰＲＳ）和傅里叶变换红外光谱（ＦＴＩＲ）研究了三种不同成因电气石单晶的振动谱学特征。ＰＲＳ研究表明电气石结构中三个阴离子团（即［Ｓｉ６Ｏ１８］＾１２－、［ＢＯ３］＾３－、［ＯＨ］＾－）的喇曼谱在平行ｃ轴方向（／／ＮＥ）比垂直ｃ轴方向（／／ＮＯ）敏锐，而且［ＯＨ］＾－喇曼光谱只在平行ｃ轴的ＰＲＳ中才观察到。不同成因电气石中［ＯＨ］＾－占位不同。结合ＦＴＩＲ研究发现在伟晶型和热液型的     

阴极发光和红外光谱技术在金刚石研究中的应用

总结了阴极发光（ＣＬ）及傅立叶变换红外光谱（ＦＴＩＲ）技术在金刚石研究中的应用。ＣＬ图像可以揭示金刚石的内部结构、生长机制、生长阶段及过程,提供塑性变形及是否含有ＣＯ２的信息,验证和解释微区ＦＴＩＲ分析、稳定同位素及地质年代研究的结果,为天然金刚石和合成金刚石的区分提供关键证据。合成金刚石的实验研究表明,氮的不同聚集态丰度值是聚集温度ＴＮＡ、金刚石存留时间ｔＭＲ及氮丰度值的函数,利用地质信息和ＦＴ     

生物成因与无机成因文石的FTIR光谱区别

对16种贝壳交叉页片层中生物成因文石的FT IR谱进行测量,并与无机成因文石进行对比和统计分析后,首次发现生物成因与无机成因文石的FT IR光谱有明显可区分的特征,生物成因文石2ν带(面外弯曲振动)频率平均值为863.4 cm-1,而无机成因文石该带的平均值为855.5 cm-1,两者频率位移达7.9 cm-1。因此文石的2ν带可作为指纹带鉴别生物和无机成因文石。     

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.     

Location and quantitative analysis of OH in coesite

 The incorporation of hydrogen (deuterium) into the coesite structure was investigated at pressures from 3.1 to 7.5 GPa and temperatures of 700, 800, and 1100 °C. Hydrogen could only be incorporated into the coesite structure at pressures greater 5.0 GPa and 1100 °C . No correlation between the concentration of trace elements such as Al and B and the hydrogen content was observed based on ion probe analysis (1335 ± 16 H ppm and 17 ± 1 Al ppm at 7.5 GPa, 1100 °C). The FTIR spectra show three relatively intense bands at 3575, 3516, and 3459 cm⁻¹ (ν₁ to ν₃, respectively) and two very weak bands at 3296 and 3210 cm⁻¹ (ν₄ and ν₅, respectively). The band at 3516 cm⁻¹ is strongly asymmetric and can be resolved into two bands, 3528 (ν_2a) and 3508 (ν_2b) cm⁻¹, with nearly identical areas. Polarized infrared absorption spectra of coesite single-crystal slabs, cut parallel to (0 1 0) and (1 0 0), were collected to locate the OH dipoles in the structure and to calibrate the IR spectroscopy for quantitative analysis of OH in coesite (ɛ _{i ,tot}=190 000 ± 30 000 l mol⁻¹ _H2O cm⁻²). The polarized spectra revealed a strong pleochroism of the OH bands. High-pressure FTIR spectra at pressures up to 8 GPa were performed in a diamond-anvil cell to gain further insight into incorporation mechanism of OH in coesite. The peak positions of the ν₁, ν₂, and ν₃ bands decrease linearly with pressure. The mode Grüneisen parameters for ν₁, ν₂, and ν₃ are −0.074, −0.144 and −0.398, respectively. There is a linear increase of the pressure derivatives with band position which follows the trend proposed by Hofmeister et al. (1999). The full widths at half maximum (FWHM) of the ν₁, ν₂, and ν₃ bands increase from 35, 21, and 28 cm⁻¹ in the spectra at ambient conditions to 71, 68, and 105 in the 8 GPa spectra, respectively. On the basis of these results, a model for the incorporation of hydrogen in coesite was developed: the OH defects are introduced into the structure by the substitution Si^4+(Si2)+4O²⁻= ^[4]□^(Si2) + 4OH⁻, which gives rise to four vibrations, ν₁, ν_2a, ν_2b, and ν₃. Because the OH(D)-bearing samples do contain traces of Al and B, the bands ν₄ and ν₅ may be coupled to Al and/or B substitution. Received: 19 December 2000 / Accepted: 23 April 2001     

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.     

Induced modifications of kaolinite under ionizing radiation: an infrared spectroscopic study

Radiation effects on kaolinite were investigated using He⁺ ions of 1.5 MeV at radiation doses up to 4.3 × 10⁸ Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 × 10¹⁶ spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects.     

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.     

Ground-based FTIR Measurements with High Temporal Resolution

We outline how ground-based Fourier transform infrared (FTIR) measurements of stratospheric trace species, obtained with high temporal resolution, could be used to detect filaments of polar vortex air at mid-latitudes and therefore test high spatial resolution chemical transport models (CTMs). Vertical column abundances of HCl, ClONO2, HNO3, N2O and HF have been obtained from FTIR solar absorption measurements made throughout the day from Aberdeen, UK (57°N, 2°W) on several days during winter/spring 1993/94 and 1994/95. The short-timescale ( 2 hours) variability observed in the columns is attributed to real atmospheric variations and is often associated with the passage of high latitude air over Aberdeen. This is confirmed by 3D modelling studies which qualitatively reproduce and rationalise the observed changes in the column data on January 19 1994, January 20 1995 and February 26 1995. We describe the viewing geometry of ground-based FTIR measurements and we suggest a measurement strategy which should maximise the information retrieved on horizontal gradients in stratospheric trace species columns from FTIR measurements.