土壤粒径的光谱响应特性研究

以实验室制备的5个不同粒径水平的土壤样本和室内高光谱数据为基础,通过对光谱数据进行重采样、数学变换等预处理并进行单因素方差分析、相关性分析和回归分析,探讨土壤粒径的高光谱特性,建立了光谱数据预测土壤粒径的校正模型。结果表明,土壤粒径对反射光谱有显著的影响,波长越长影响越大;在全波段范围内土壤粒径和光谱数据都呈负相关关系,对原始光谱数据进行微分变换能增加其与土壤粒径的相关性;以反射率一阶微分建立的回归模型为反演土壤粒径的最佳模型,其建模决定系数■、预测决定系数■、预测相对偏差RPD分别为0.666,0.653,2.043,预测均方根误差RMSE为0.175。     

RESOLUTION OF MULTICOMPONENT FLUORESCENT MIXTURES BY ANALYSIS OF THE EXCITATION-EMISSION-FREQUENCY ARRAY

Fluorescence lifetime provides a third independent dimension of information for the resolution of totalluminescence spectra of multicomponent mixtures.The incorporation of this parameter into theexcitation-emission matrix(EEM)by the phase modulation technique results in a three-dimensionalexcitation-emission-frequency array (EEFA).Multicomponent analysis based on the three-dimensionalEEFA brings a qualitative change for the resolved spectra,i.e.individual spectra can be uniquely resolved,which is impossible with any two-dimensional analysis.In this paper we present a method for analyzingthe EEFA.We show mathematically that with the three-dimensional analysis of the EEFA individualspectra and lifetimes can be obtained.Our algorithm is developed in mathematical detail and isdemonstrated by its application to a two-component mixture.     

Characterisation of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra

Tobelite (NH₄) Al₂ [AlSi₃O₁₀] (OH)₂, the ammonium analogue of muscovite, and its deuterated form ND₄-tobelite (ND₄) Al₂ [AlSi₃O₁₀] (OD)₂ have been synthesised at 600?°C and 200 and 500 Mpa using a well homogenised, stoichiometric SiO₂-Al₂O₃ oxide mix with Al₂O₃ in excess of 5 mol% and a 25% NH₃ solution whose relative abundance was such that the amount of NH₄ ⁺ stoichiometrically available was in excess of 50%. Characterisation of both tobelite and ND₄-tobelite using IR-spectroscopy, Rietveld refinement of X-ray powder diffraction data, and electron microprobe analysis indicate that, similar to K⁺ in muscovite, the NH₄ ⁺ or ND₄ ⁺ molecule occupies the interlayer site. IR absorption bands caused by NH₄ ⁺ and ND₄ ⁺ can be explained, to a very good approximation, on the basis of T_d symmetry. Nevertheless, substantial line broadening and the occurrence of shoulders indicate a deviation from ideal T_d symmetry. However, even at 77?K, no discrete splitting of the degenerate states could be confirmed. The OH stretching frequencies observed for synthetic tobelite are quite similar to those for muscovite, indicating that the replacement of K⁺ by NH₄ ⁺ has no effect. The low FWHH of the OH bands indicate that the hydroxyl groups are well ordered within the structure. Rietveld refinement of tobelite and ND₄-tobelite indicates that all samples synthesised consist of the 3 different mica polytypes which are typical of muscovite – namely 1M (C2/m), 2M ₁ (C2/c) and 2M ₂ (C2/c). Tobelite and ND₄-tobelite synthesised at 500 Mpa principally contain the 1M polytype, whereas the principle polytype for ND₄-tobelite synthesised at 200 Mpa, is 2M ₂. Rietveld refinement of X-ray diffraction spectra for tobelite synthesised at 200 Mpa was problematic due to the very broad FWHH of the X-ray peaks indicating poor crystallinity. In comparision to synthetic muscovite, the cell dimensions observed for tobelite and its deuterated analogue are quite similar except for the lattice constant c. Due to the larger radius of NH₄ ⁺ or ND₄ ⁺ compared to K⁺ cation, the c-direction is expanded form 10.275 Å in muscovite to approximately 10.540 Å in tobelite and ND₄-tobelite.     

Crystal chemistry of tremolite–tschermakite solid solutions

Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr₂ solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (X_ts=0.54). Different cummingtonite concentrations (X_cum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 ų were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm^?1 (I), 3633–3664 cm^?1 (II) and 3526–3633 cm^?1 (III). Assuming ^[6]Al substitution at M2 and/or M3 and ^[4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si⁴⁺ at T1 and one or two Al³⁺ at M2 and/or M3_far, II: one Al³⁺ at T1 and one to three Al³⁺ at M2 and/or at M3_far, III: either Al³⁺ on M3_near and/or two Al³⁺ on T1 and additional one to four Al³⁺ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

含钒石煤的穆斯堡尔谱研究

本文收集了我国湘鄂淅地区含钒石煤样品,使用化学分析和穆斯堡尔谱方法,测定和研究了石煤中钒铁的赋存方式和价态,以及不同焙烧温度下钒铁价态变化等。初步研究表明,石煤中钒铁价态及价态变化的测定,对含钒石煤中钒铁矿物和成因研究,钒的提取和石煤的综合利用有重要意义。     

Sorption Characteristics of Rare Earth Element Eu^3＋ onto Silica-Water Interfaces Studied by Fluorescence Spectroscopy

The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for Ph ranges of 1-8.5 and an initial Eu concentration (Ceu) of 2×10-4 M. The sorption rate of Eu was initially low, but significantly increased at Ph>4. The sorption density of Eu species on a silica surface was ～1.58×10-7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at Ph=～5.8. The sorbed Eu species at Ph<6 is aquo Eu3 , which is sorbed onto silica-water interfaces as an outer-sphere complex at Ph<5, but may be sorbed as an inner-sphere bidentate complex at 5相似文献   

Ab-initio calculations of the proton location in topaz-OH,Al<Subscript>2</Subscript>SiO<Subscript>4</Subscript>(OH)<Subscript>2</Subscript>

The position of hydrogen in the structure of topaz-OH was determined by means of ab-initio quantum-mechanic calculations. Static lattice energy calculations predict the existence of four non-equivalent positions of protons, which are characterized by O4–H1... O1, O4–H2... O2, O4–H3... O3 and O4–H4... O4 hydrogen bonds. The distribution of the protons between positions of local equilibrium is controlled by the proton–proton avoidance rule and the strength of the hydrogen bonds. The most favourable configuration of hydrogen atoms is achieved for adjacent protons, which form O4–H3... O3 and O4–H4... O4 hydrogen bonds, respectively. The thermal excitation of atoms at a temperature of 55 K is large enough for the hydrogen atoms occasionally to change their positions to form O4–H1... O1 and O4–H2... O2 bonds. At ambient pressures and higher temperatures the protons are in a dynamic exchange between the allowed positions of local minima. As a consequence, for nearly room-temperature conditions, the dynamic change between different structural configurations leads to the violation of all possible symmetry elements and with that to space group #E5/E5#1. The flipping of the protons between different sites is achieved by simple rotation of the OH-dipole and does not produce any significant distortion of the framework of topaz, whose symmetry remains that of the space group Pbnm. Therefore, no reduction of symmetry has been observed in former X-ray studies on topaz-OH. Calculated IR absorption spectra of topaz-OH were found to be in good agreement with measured spectra. According to the calculations, the two favourable configurations of protons might correspond to the measured peak splitting within the OH-stretching range. An experimentally observed low-frequency band at 3520 cm^–1 was assigned to the OH-stretching of the O4–H3... O3 bond, while the band at 3600 cm^–1 was attributed to OH-stretching of the O4–H4... O4 hydrogen bond. The broad peak in FAR-IR frequency range at 100–150 cm^–1 is attributed to the stretching of H3... O3 and H4... O4 contacts. The rate of proton exchange at 670 K among different sites was estimated by ab-inito molecular dynamic simulations. The calculations predict that flipping of adjacent protons between O4–H3... O3 and O4–H4... O4 bonds at 670 K occur at a rate of about 1.96 THz.     

The project “spice”

Proposed to both the French and the European Space Agency as one possible small mission, SPICE is a project for a dedicated small satellite for a near-IR spectroscopic all-sky survey. The instrument would cover the spectral range 1.8 - 3.6µm, possibly extended to 1.8 - 7µm, at a resolution of 100, with pixels of 1 arc-min. The excellent sensitivity (0.02 MJy sr-1) results from: i) the quasi-zero level of background due to the efficient passive cooling of the whole experiment; ii) the use of large format arrays; iii) the non-stop observing mode (drift-scanning). The spectral domain, complementing the one of ISO, partially opaque from the ground, is specially rich in spectral features tracing stars and all components of the Interstellar Medium (molecular, atomic and ionized gas, dust). With a cooling below 80 K of the focal instrument, then it becomes possible to consider doubling the spectral domain and to cover the whole 1.8 - 7µm range.     

The C1XS X-ray Spectrometer on Chandrayaan-1

The Chandrayaan-1 X-ray Spectrometer (C1XS) is a compact X-ray spectrometer for the Indian Space Research Organisation (ISRO) Chandrayaan-1 lunar mission. It exploits heritage from the D-CIXS instrument on ESA's SMART-1 mission. As a result of detailed developments to all aspects of the design, its performance as measured in the laboratory greatly surpasses that of D-CIXS. In comparison with SMART-1, Chandrayaan-1 is a science-oriented rather than a technology mission, leading to far more favourable conditions for science measurements. C1XS is designed to measure absolute and relative abundances of major rock-forming elements (principally Mg, Al, Si, Ca and Fe) in the lunar crust with spatial resolution ?25 FWHM km, and to achieve relative elemental abundances of better than 10%.