浙江缙云斜发沸石水的核磁共振分析

本文应用宽线NMR技术,结合红外测定,研究了缙云斜发沸石中水的结构类型、存在状态、运动特征和热稳定性。结果表明:缙云斜发沸石中的沸石水按其运动特性可以分为受阻旋转水、自由旋转水和自扩散运动水三种类型,它们以谱线中分裂的双线和线宽不同的单峰相区别。低温时,受阻旋转运动的水在晶格中转变为刚性配置。其脱水次序决定于各类型水与沸石结构骨架键合的强弱,脱水是连续的。研究显示缙云斜发沸石的结构骨架相当疏宽,骨架对水分子的吸引力没有严格的方向性,这一特性有利于阳离子的交换。     

Infrared estimates of aliphatic kerogen carbon in sedimentary rocks

An infrared routine has been developed to estimate the aliphatic portion of kerogen carbon in sedimentary rocks. The procedure does not require isolation of the organic matter and is based on a computer-assisted determination of global band areas in the region of the aliphatic carbon-hydrogen stretching vibrations around 2900cm⁻¹. From these integrated absorptions the amount of aliphatic carbon C_al (mg of aliphatic carbon per gram of solvent-extracted rock) is calculated by means of a calibration with model rocks. Carbonate overtones which interfere in the case of limestones are eliminated by comparison to a CaCO₃ standard.The method has been applied to rocks containing kerogens of different types and maturities at TOC levels of 0.5 to 12%. The aliphatic carbon concentrations range from 0.5 to 60mg·g⁻¹ and correlate reasonably well with the residual genetic potentials of the rocks as measured by S₂ values from Rock-Eval pyrolysis. The ratio S₂/C_al is found to decrease with burial depth reflecting a maturity enhanced conversion of aliphatic carbon to fixed aromatic carbon under Rock-Eval conditions.     

白云鄂博碳酸岩脉的显微共聚焦激光拉曼光谱分析

白云鄂博矿区发育的脉状稀土碳酸岩，由于其结晶迅速，矿物颗粒细微，其中的微小矿物的鉴定一直是一个难题。应用显微共聚焦激光拉曼光谱仪则能较好地解决这一问题。研究表明，白云鄂博地区存在富稀土白云质岩浆碳酸岩脉，早期阶段形成碱性长石和铁白云石，无稀土矿化；铁白云石常常出溶铁质而自身则形成方解石。霓石和方解石形成略晚，常常与氟碳铈矿等稀土矿物共生，出现强烈的稀土矿化；而无解理的方解石则形成于更晚的岩浆期后热液阶段，发育大量的流体包裹体，并出现强烈的铌、稀土矿化。铌铁矿分布在氟碳铈矿中和赤铁矿边缘，为热液交代作用的产物。早期结晶的矿物如碱性长石、铁白云石稀土矿化弱，岩浆晚期分异出大量的流体相，稀土元素和Sr等进入岩浆热液中，并在热液结晶矿物中富集，甚至在非平衡结晶的石英中产生强烈的稀土矿化。结合岩相学显微观察，显微拉曼探针很好的揭示了这一地质过程。同时为白云鄂博矿床铌、稀土矿化的热液交代成因提供了依据。     

利用漫反射光谱鉴定红粘土中针铁矿和赤铁矿

针铁矿(Gt)和赤铁矿(Hm)是广泛存在于土壤和沉积物中的重要铁矿物。这两种矿物在土壤和沉积物中含量很低,常规的测试手段很难有效地测定其含量。利用反射光谱联合加热处理的方法,可对土壤及沉积物样品中针铁矿和赤铁矿进行定性或半定量测定。实验结果显示,样品加热到300℃后,针铁矿的反射光谱的一阶导数特征峰发生了变化,赤铁矿的一阶导数特征峰却没有明显的变化。因此加热前后样品反射光谱一阶导数的变化取决于针铁矿和赤铁矿的含量。利用这种方法估计黄土高原第三纪红粘土样品中的赤铁矿含量约为0.3%～0.4%,针铁矿含量约为0.5%～1%。     

Raman spectra of methane hydrate up to 86 GPa

High-pressure Raman studies of methane hydrate were performed using a diamond anvil cell in the pressure range of 0.1–86 GPa at room temperature. Raman spectra of the methane molecules revealed that new softened intramolecular vibration mode of ν ₁ appeared at 17 GPa and that the splitting of vibration mode of ν ₃ occurred at 15 GPa. The appearance of these two modes indicates that an intermolecular attractive interaction increases between the methane molecules and the host water molecules and between the neighboring methane molecules. These interactions might result in the exceptional stability of a high-pressure structure, a filled ice Ih structure (FIIhS) for methane hydrate, up to 40 GPa. At 40 GPa, a clear change in the slope of the Raman shift versus pressure occurred, and above 40 GPa the Raman shift of the vibration modes increased monotonously up to 86 GPa. A previous XRD study showed that the FIIhS transformed into another new high-pressure structure at 40 GPa. The change in the Raman spectra at 40 GPa may be induced by the transition of the structure.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy,X-ray single-crystal diffractometry,and electronic structure calculations on natural alexandrite

Natural alexandrite Al₂BeO₄:Cr from Malyshevo near Terem Tschanka, Sverdlovsk, Ural, Russia, has been characterized by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe, X-ray single-crystal diffractometry and by electronic structure calculations in order to determine oxidation state and location of iron. The sample contains 0.3 wt% of total iron oxide. The ⁵⁷Fe Mössbauer spectrum can be resolved into three doublets. Two of them with hyperfine parameters typical for octahedrally coordinated high-spin Fe³⁺ and Fe²⁺, respectively, are assigned to iron substituting for Al in the octahedral M2-site. The third doublet is attributed to Fe³⁺ in hematite. Electronic structure calculations in the local spin density approximation are in reasonable agreement with experimental data provided that expansion and/or distortion of the coordination octahedra are presumed upon iron substitution. The calculated hyperfine parameters of Fe³⁺ are almost identical for the M1 and M2 positions, but the calculated ligand-field splitting is by far too large for high-spin Fe³⁺ on M1.     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Analysis of Physical and Chemical Parameters for Discrimination of Water Origin in a Hydroelectric Reservoir

Seventeen physical and chemical parameters were obtained from a hydroelectric reservoir located in a tropical region in the south of Brazil. Multivariate Principal Component Analysis (PCA) and Hierarchical Group Analysis (HGA) were used to identify the parameters discriminating the origin of water from the Tibagi and the Primeiro de Maio River, after it has passed the mixing region. The study was conducted during the dry and rainy seasons in July 2002 and February 2003 at three depths and three sampling sites located 0, 5, and 10 km away from the mixing region. The statistical methods showed to be appropriate for identifying the contribution of each tributary in the water mixing site of a complex water system. The most important discriminating parameter was the absorbance relation A(253 nm)/A(203 nm), followed by the concentrations of Fe(III), Mn(III), and Ni(II). An anthropogenic interference was found in the reservoir due to high Ni(II) and orthophosphate concentrations caused by a nearby town sewage discharge. The interference was more important during the dry periods due to the lower dispersion of the pollutants. Urgent initiatives should be taken from the state government to build treatment stations for the wastewater of the small cities around the Capivara hydroelectric reservoir to prevent the drinking water quality from deteriorating.     

Use of high spectral resolution remote sensing to determine leaf palatability of eucalypt trees for folivorous marsupials

In this study we assess the feasibility of remotely measuring canopy biochemistry, and thus the potential for conducting large-scale mapping of habitat quality. A number of studies have found nutrient composition of eucalypt foliage to be a major determinant of the distribution of folivorous marsupials. More recently it has been demonstrated that a specific group of secondary plant chemicals, the diformylphloroglucinols (DFPs), are the most important feeding deterrents, and are thus vital determinants of habitat quality. We report on the use of laboratory spectroscopy to attempt to identify one such DFP, sideroxylonal-A, in the foliage of Eucalyptus melliodora, one of the few eucalypt species browsed by folivorous marsupials. Reflectance spectra were obtained for freeze-dried, ground leaves using near infrared spectroscopy (NIRS) and for both oven-dried and fresh whole leaves using a laboratory-based (FieldSpec) spectroradiometer. Modified partial least squares (MPLS) regression was used to develop calibration equations for sideroxylonal-A concentration based on the reflectance spectra transformed as both the first and second difference of absorbance (Log 1/R). The predictive ability of the calibration equations was assessed using the standard error of calibration statistic (SECV). Coefficients of determination (r²) were highest for the ground leaf spectra (0.98), followed by the fresh leaf and dry leaf spectra (0.94 and 0.87, respectively). When applied to independent validation sub-sets, sideroxylonal-A was most accurately predicted from the ground leaf spectra (r² = 0.94), followed by the dry leaf and fresh leaf spectra (0.72 and 0.53, respectively). Two spectral regions, centred on 674 nm and 1394 nm, were found to be highly correlated with sideroxylonal-A concentration for each of the three spectral data sets studied. Results from this study suggest that calibration equations derived from modified partial least squares regression may be used to predict sideroxylonal-A concentration, and hence leaf palatability, of Eucalyptus melliodora trees, thereby indicating that the remote estimation of habitat quality of eucalypt forests for marsupial folivores is feasible.     

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