胜利油气区有机包裹体研究及其在油气勘探中的应用

应用显微光度术、显微傅立叶红外光谱（Ｍｉｃｒｏ－ＦＴ．ＩＲ）和飞行时间二次离子质谱（ＴＯＦ－ＳＩＭＳ）等原位微分析技术并结合均一温度测量对胜利油气区下第三系沙河街组沙三段中有机包裹体进行了研究。区分出两类有机包裹体，即原生有机包裹体和次生有机包裹体。结果表明两类有机包裹体特征不同，二者物质组成、有机质成分及化学结构、热演化程度等差别也较大。结合地质分析表明原生有机包裹体是沙三段烃源岩生成烃类运移产物，具“自生自储”特点，而次生有机包裹体是沙四段烃源岩生成的烃类二次运移的产物。沙三段是沙河街组油气运移和聚集的主要层位，因而是寻找油气资源的主要目标层。研究表明，有机包裹体是研究油气生成、运移、聚集和演化等成藏系统最有效的手段之一，在油气勘探中有重要的应用意义。     

Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

Interannual sea level variability in the South China Sea and its response to ENSO

Sea level observed by altimeter during the 1993–2004 period, thermosteric sea level from 1945 through 2004, and tide gauge records are analyzed to investigate the interannual variability of sea level in the South China Sea (SCS) and its relationship with ENSO (El Niño and Southern Oscillation). Both the interannual variations of the observed sea level and the thermosteric sea level are closely related to ENSO. An ‘enigma’ that the SST and sea level in the SCS have inverse response to ENSO is revealed. It is found that the thermosteric sea level has an excellent correspondence to seawater temperature at 100 m depth, and their variations are unsynchronized to SST. Detailed analysis denotes that the warming of seawater occurs only in the upper 75 m during and after the mature phase of El Niño, while the cooling appears in the layers deeper than 75 m during El Niño years. The volume transports between the SCS and the adjacent oceans and the anomalous Ekman pumping contribute a lot for the sea level fall in the developing stage of El Niño, while the mass exchange, which is dominated by precipitation, plays a more significant role in the following continuous negative sea level anomalies.     

Elastic collisions in ion irradiation experiments: A mechanism for space weathering of silicates

Ion irradiation experiments have been performed on silicates (bulk samples) rich of olivine, pyroxene, and serpentine to simulate the effects of space weathering induced on asteroids by solar wind ions. We have used different ions (H⁺, He⁺, Ar⁺, Ar²⁺) having different energies (from 60 to 400 keV) to weather the samples, probed by Raman spectroscopy and UV-vis-NIR reflectance spectroscopy. All the irradiated materials have shown reddening and darkening of reflectance spectra in the 0.25-2.7 μm spectral range. We have found that the increase of the spectral slope of the continuum across the 1-μm band is strongly related with the number of displacements caused by colliding ions because of elastic collisions with the target nuclei. The spectral slopes have been compared, at increasing ion fluence, with those from irradiated Epinal meteorite. We show that formation of nuclear displacements by solar wind ion irradiation is a physical mechanism that reddens the asteroidal surfaces on a time-scale lower than 10⁶ years.     

H3 as a trap for noble gases: 1—The case of Argon

The possibility of H₃⁺ playing a role as a sink for noble gases has been investigated in the case of Argon. Elaborate quantum methods (ab initio Coupled Cluster and density functional BH&HLYP levels of theory) have been shown to reproduce the rotational constants within 0.3% together with the only known IR frequency on the test case of Ar…D₃⁺. Dissociation energies of (Ar)_n…H₃⁺ as a function of cluster size, i.e. 7.2 (n=1), 3.7 (n=2), 3.6 (n=3), 1.6 (n=4), 1.7 (n=5) kcal/mol, follow the pattern established experimentally for (Ar)_n…H₃⁺ and (H₂)_n…H₃⁺ series. Rotational constants and harmonic frequencies of (Ar)_n…H₃⁺ (n=1-3) are presented.     

Heliocentric evolution of the degradation of polyoxymethylene: Application to the origin of the formaldehyde (H2CO) extended source in Comet C/1995 O1 (Hale-Bopp)

The H₂CO production rates measured in Comet C/1995 O1 (Hale-Bopp) from radio wavelength observations [Biver, N., and 22 colleagues, 2002a. Earth Moon Planets 90, 5-14] showed a steep increase with decreasing heliocentric distance. We studied the heliocentric evolution of the degradation of polyoxymethylene (formaldehyde polymers: (CH₂O)_n, also called POM) into gaseous H₂CO. POM decomposition can indeed explain the H₂CO density profile measured in situ by Giotto spacecraft in the coma of Comet 1P/Halley, which is not compatible with direct release from the nucleus [Cottin, H., Bénilan, Y., Gazeau, M.-C., Raulin, F., 2004. Icarus 167, 397-416]. We show that the H₂CO production curve measured in Comet C/1995 O1 (Hale-Bopp) can be accurately reproduced by this mechanism with a few percents by mass of solid POM in grains. The steep heliocentric evolution is explained by the thermal degradation of POM at distances less than 3.5 AU. This study demonstrates that refractory organics present in cometary dust can significantly contribute to the composition of the gaseous coma. POM, or POM-like polymers, might be present in cometary grains. Other molecules, like CO and HNC, might also be produced by a similar process.     

Theoretical survey of the NH+CH3 potential energy surface in relation to Titan atmospheric chemistry

This paper looks at the possibilities opened by reaction of NH with methyl radical. A general survey of the potential surface by ab initio Möller-Plesset (MP2) and density functional theory has been performed, including determination of transition states on the pathways considered and vibrational analysis of all stationary points. Energetical data have been obtained using coupled cluster molecular orbital methods (CCSD(T)). It is shown that HCN is not formed from these starting reactants, but that CH₂NH, a possible precursor of tholins and of prebiotic compounds through hydration is the major product.     

上海天文台2004年度的科研工作

简要回顾了中国科学院上海天文台2004年科研及相关工作情况。     

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

Low temperature (39-298 K) kinetics study of the reactions of the C4H radical with various hydrocarbons observed in Titan's atmosphere

The reaction kinetics of the butadinyl radical, C₄H, with various hydrocarbons detected in the atmosphere of Titan (methane, ethane, propane, acetylene, ethene and methylacetylene) are studied over the temperature range of 39-298 K using the Rennes CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme) apparatus. Kinetic measurements were made using the pulsed laser photolysis—laser induced fluorescence technique. The rate coefficients, except for the reaction with methane, all show a negative temperature dependence and can be fitted with the following expressions over the temperature range of this study: ; ; , , . These expressions are not intended to be physically meaningful but rather to provide an easy way to introduce experimental results in photochemical models. They are only valid over the temperature range of the experiments. Possible channels of these reactions are discussed as well as possible consequences of these results for the production of large molecules and hazes in the atmosphere of Titan. These results should also be considered for the photochemistry of Giant Planets.