Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.     

垂直气柱中大气微量成分总含量的反演

提出了一种利用地面中等光谱分辨率的太阳红外光谱反演整层大气中某几种微量成分总含量的方法,用逐线积分（ Ｌ Ｂ Ｌ） 法计算整层大气分子吸收,采用差分吸收法测量太阳红外光谱得到实际大气中微量成分的吸收,用最大似然法反演出微量成分的总量。详细分析了这种方法的可行性和反演精度,数值模拟分析和实际测量表明该方法有较高的精度,已把该方法用于监测实际大气中甲烷和水汽总含量的变化。     

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.     

两种不同颜色C6H4(NH2)2·2HCl的合成及光谱研究

室温下,于CH3OH和H2O的混合溶剂中,钨酸钠存在下邻苯二胺和盐酸反应合成了棕色和红色两种不同颜色的C6H4(NH2)2.2HCl晶体,X-射线单晶衍射分析,晶体属单斜晶系,空间群为C2/c,a=0.7339(2)nm,b=1.4535(5)nm,c=0.8009(3)nm,β=94.041(5)°,V=0.8522(5)nm3,z=4,R1=0.0247,WR2=0.0684。奇特的是棕色晶体与红色晶体均为邻苯二胺盐酸盐,具有相同的晶体结构和IR光谱,但UV光谱呈现出差异。     

热红外极轨卫星地震监测系统综合技术研究

以2003年架设的NOAA／FY极轨卫星数据地面接收站为基础,针对NOAA系列卫星．采用分布式处理方案,设计并建立了地震热红外卫星监测业务运行系统。系统主要功能包括：卫星数据的接收、处理、归档、查询、发布;自动生成全国夜晚地表亮温图像、全国白天彩色合成图像、全国每旬无云地表亮温图像等专题数据库产品;对任意选定的监测区进行热红外亮温动态跟踪和异常警示;实现了直观的无人值守的准实时自动化处理以及远程管理和数据检索。通过对地震热红外卫星监测业务运行系统的研究和开发,在数据标定、辐射校正、图像预处理、专题产品的生成与管理等方面取得了宝贵的经验,为我国地震卫星地面数据接收、处理系统的建立奠定了基础。     

Near-infrared spectroscopy of 133P/Elst-Pizarro

Comet 133P/Elst-Pizarro, known to be a main-belt asteroid with a cometary activity, was observed with the near-infrared integral field spectrograph SINFONI at the 8.2-m Very Large Telescope in J, H, and K bands during its 2007 perihelion passage. The goal of these observations was to attempt detection of water ice absorption bands. We present here the details of the data processing, the results of these observations, and our compositional modeling of the final spectrum. No water ice absorptions were detected within the noise of the spectrum but we show that this spectrum is compatible with a reasonable near-infrared albedo value of 7-10% and a mixture of water ice, black carbon, Tholin and silicates. This interpretation, nevertheless, is not unique.     

Radiolysis of sulfuric acid, sulfuric acid monohydrate, and sulfuric acid tetrahydrate and its relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H₂SO₄), sulfuric acid monohydrate (H₂SO₄·H₂O), and sulfuric acid tetrahydrate (H₂SO₄·4H₂O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H₂O, SO₂, (S₂O₃)_x, H₃O⁺, , and . At high radiation doses, we find that H₂SO₄ molecules are destroyed completely and that H₂SO₄·H₂O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H₂SO₄, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H₂SO₄ or H₂SO₄·H₂O, the loss of H₂SO₄·4H₂O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa’s surface, we speculate that the variations in SO₂ concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.     

Formation of radical species in photolyzed CH4:N2 ices

We report photochemical studies of thin cryogenic ice films composed of N₂, CH₄ and CO in ratios analogous to those on the surfaces of Neptune’s largest satellite, Triton, and on Pluto. Experiments were performed using a hydrogen discharge lamp, which provides an intense source of ultraviolet light to simulate the sunlight-induced photochemistry on these icy bodies. Characterization via infrared spectroscopy showed that C₂H₆ and C₂H₂, and HCO are formed by the dissociation of CH₄ into H, CH₂ and CH₃ and the subsequent reaction of these radicals within the ice. Other radical species, such as C₂, , CN, and CNN, are observed in the visible and ultraviolet regions of the spectrum. These species imply a rich chemistry based on formation of radicals from methane and their subsequent reaction with the N₂ matrix. We discuss the implications of the formation of these radicals for the chemical evolution of Triton and Pluto. Ultimately, this work suggests that , CN, HCO, and CNN may be found in significant quantities on the surfaces of Triton and Pluto and that new observations of these objects in the appropriate wavelength regions are warranted.     

常见绿松石品种特征及充填处理的鉴定

总结了我国市场上大量常见的不同产地的天然绿松石的特征,同时对比我国市场常见的充填处理绿松石的特征,研究了天然与充填处理绿松石的一般鉴别特征,发现处理绿松石的颜色深浅、颜色分布、包裹体、外观与天然绿松石均有较大的区别。还利用红外光谱对天然的和充填处理的绿松石进行了测试,发现充填处理绿松石在1 735、1 600、1 500 cm^-1附近可见吸收峰,表明绿松石内部充填了人工类树脂,可作为鉴定充填处理绿松石的有力证据。     

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).