Radiation stability of organic matter in liquid and frozen H2O, NH3 and water-ammonia mixtures

The redox properties of irradiated liquid and frozen H₂O, NH₃ and H₂O/NH₃ mixtures at 298 K and 77 K, resp., towards some simple organic molecules have been checked by injecting carrierfree ¹¹C atoms and analyzing their chemical state by means of radiochromatography. The reactions and the stability of organic products versus radiation dose (in this study by MeV protons) depend on temperature, phase state, mobility of radicals, their concentration and reactivity. Especially dangerous are the reactive OH and O₂H radicals which oxidize organic material to inorganic CO₂. Highest stability has been found at low temperatures (solid state, reduced mobility of radicals) and for systems containing H-donors (H₂O/NH₃ mixtures), which reduce the concentration of oxidizing radicals. The fact that many bodies in space consist of H₂O-ice with NH₃ and CH₄ additives at temperatures between 10 and 150 K is promising in view of the survival of organic matter under high doses of radiation.     

Chemical and biological evolution in space

Astronomical infrared spectra are used to confirm the existence of complex organic molecules produced by ultraviolet photoprocessing of interstellar grain mantles. This material is shown to be the major component of the interstellar grains between the sun and the galactic center and, by inference, constitutes more than 10 million solar masses — or close to one part in a thousand of the entire mass of the milky way galaxy. It may be demonstrated that the primitive chemistry of the earth's surface was dominated by these extraterrestrial molecules after aggregated into comets if the rate of comet impacts with the earth was comparable with that required to account for the extinction of species over the past 300 million years.

Ultraviolet irradiation of bacterial spores has been studied for the first time under simulated interstellar conditions. The inactivation time predicted for the less dense regions of space is at most several hundred years. Within molecukar clouds it is shown on theoretical and experimental grounds that this t the estimated cloud. However survival of spores during their initial exposure to the solar ultraviolet presents a problem for panspermia because it requires that in the process of ejection from the earth's surface they must be enclosed within a cocoon (or mantle) of ultraviolet absorbing material of 0.6 μm thickness. Thus, although panspermia can not be rejected on the basis of lack of interstellar survival there may remain insurmountable obstacles to its occuring because of the very special protective shield requirements during ejection from its planetary source.     

Observational astrochemistry

Astronomers have identified some 70 molecular species in dense interstellar clouds and the envelopes expelled by evolved stars. Some 75% of these are organic, including molecules with up to 13 atoms and with weights up to 147 daltons. Elements found in interstellar compounds include H, C, N, O, S, Si, and probably Cℓ. A recent addition to the list of interstellar molecules is the first hydrocarbon ring, cyclopropenylidene (C₃H₂). Current research in astrochemistry is concentrating on the determination of accurate chemical abundances as a function of environment. Both basic similarities and intriguing differences among clouds are found, which may provide clues to processes associated with cloud evolution and star formation.     

The formation of organic molecules in astronomical ices.

An absorption feature at 3.4 micrometers has been observed in various lines-of-sight through the diffuse interstellar medium. Its position and width lead to an identification with the C-H stretching mode of solid organic material. A possible mechanism for the production of organic solids in the interstellar medium is UV photoprocessing of icy mantles which accrete on dust grains in dense clouds. Furthermore, thermally induced reactions involving formaldehyde molecules in the mantles could be an important source of organics. Laboratory simulation of these processes shows that a large variety of oxygen- and nitrogen-rich species may be produced. It is shown that the occurrence of periodic transient heating events plays an important role in the production of organic material in the ice mantles. Finally, it is pointed out how future missions like the Infrared Space Observatory (ISO) as well as analysis of comet material by Rosetta may be able to clarify the nature and evolution of interstellar organics.     

Complex organics in laboratory simulations of interstellar/cometary ices.

We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.     

Interstellar hydrogen bonding

This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.     

Spectroscopic properties of polycyclic aromatic hydrocarbons (PAHs) and astrophysical implications.

PAHs (polycyclic aromatic hydrocarbons) are probably present as a mixture of neutral and ionized species and are responsible for the set of infrared emission bands in the 2-15 microns regions, which are observed in many different objects like reflection and planetary nebulae and external galaxies. PAHs are suggested to be the most abundant free organic molecules and ubiquitous in space. PAHs might also exist in the solid phase, included in interstellar ices in dense clouds. A complex aromatic network is expected on interstellar grains in the diffuse interstellar medium. The existence of an aromatic kerogen-like structure in carbonaceous meteorites and its similarity with interstellar spectra suggests a link between interstellar matter and primitive Solar System bodies.     

A fine mist of very small comet dust particles

A comet nucleus considered as an aggregate of interstellar dust would produce a mist of very finely divided (radius ～ 0.01 μm) particles of carbon and metal oxides accompanying the larger dust grains. These small particles which are very abundant in the interstellar dust size spectrum would provide substantial physical effects because of their large surface area. They may show up strongly in particle detectors on the Halley probes. A strong basis for serious consideration of these particles comes from the other evidence that interstellar dust grains are the building blocks of comets; e.g. (1) the explanation of the “missing” carbon in comets; (2) The S₂ molecule detection which suggests that the comet solid ice materials have been previously subjected to ultraviolet radiation (as are interstellar grains) before aggregation into the comet; (3) the predicted dust to gas ratio.     

Hot atoms in cosmic chemistry

High energy chemical reactions and atom molecule interactions might be important for cosmic chemistry with respect to the accelerated species in solar wind, cosmic rays, colliding gas and dust clouds and secondary knock-on particles in solids. “Hot” atoms with energies ranging from a few eV to some MeV can be generated via nuclear reactions and consequent recoil processes. The chemical fate of the radioactive atoms can be followed by radiochemical methods (radio GC or HPLC). Hot atom chemistry may serve for laboratory simulation of the reactions of energetic species with gaseous or solid interstellar matter. Due to the effective measurement of 10⁸–10¹⁰ atoms only it covers a low to medium dose regime and may add to the studies of ion implantation which due to the optical methods applied are necessarily in the high dose regime.

Experimental results are given for the systems: C/H₂O (gas), C/H₂O (solid, 77 K), N/CH₄ (solid, 77K) and C/NH₃ (solid, 77 K). Nuclear reactions used for the generation of 2 to 3 MeV atoms are: ¹⁴N(p, ) ¹¹C, ¹⁶O(p, pn) ¹¹C and ¹²C(d,n) ¹³N with 8 to 45 MeV protons or deuterons from a cyclotron. Typical reactions products are: CO, CO₂, CH₄, CH₂O, CH₃OH, HCOOH, NH₃, CH₃NH₂, cyanamide, formamidine, guanidine etc. Products of hot reactions in solids are more complex than in corresponding gaseous systems, which underlines the importance of solid state reactions for the build-up of precursors for biomolecules in space. As one of the major mechanisms for product formation, the simultaneous or fast consecutive reactions of a hot carbon with two target molecules (reaction complex) is discussed.     

Observational astrochemistry: recent results.

More than 80 molecular species have now been observed by astronomers in the dense interstellar clouds where stars and planets form or in the envelopes expelled by evolved stars. Elemental constituents of these compounds include all of the "biogenic" elements, hydrogen, carbon, nitrogen, oxygen, sulfur, and (most recently) phosphorus. In addition, silicon is found in several molecules, and a series of metal halides have recently been detected in the outflowing envelope of a nearby carbon star. Additions to the list of known interstellar molecules since the last COSPAR meeting are discussed individually. Recent measurements of the hydrogen isotopic fractionation for the cyclic molecule C3H2 are described; values up to 10,000 times the cosmic deuterium-to-hydrogen ratio are found. Knowledge of the chemical reservoirs for the major volatile elements and a comparison between observed molecular abundances and theoretical models are both discussed.     

S3 and S4 absorption cross sections in the range of 340 to 600 nm and evaluation of the S3 abundance in the lower atmosphere of Venus

S₃ absorption cross section equals 6×10⁻¹⁷ cm² at 400 nm, 6 × 10⁻¹⁹ cm² at 500 nm (less by a factor of 4 than that given by Sanko), 4×10⁻²⁰ cm² at 600 nm. That of S₄ equals 1.5 × 10⁻¹⁷ cm² at 450 nm, 8 × 10⁻¹⁷ cm² at 500 nm, and 4.7 × 10⁻¹⁷ cm² at 600 nm. Preliminary evaluation of the S₃ mixing ratio in the lower atmosphere of Venus is (8±3)×10⁻¹¹ at 5 to 25km according to the Venera 14 measurements and several times lower at the locations of the Veneras-11 and -13.     

太阳E10.7指数的反演及预报方法

针对高层大气密度预报和轨道预报业务中对新型太阳紫外辐射指数E_10.7的需求,基于TIMED-SEE观测仪器提供的0.1～105 nm太阳辐射强度数据,开展了E_10.7指数反演和中期预报研究。 E_10.7指数是太阳光谱中波长为0.1～105 nm的辐射流量,单位与F_10.7指数相同（sfu,1 sfu=10–22 W·m–2·Hz–1）。 TIMED-SEE观测仪器提供的0.1～105 nm太阳辐射强度实测值具有高时间分辨率、延迟时间短和易获得的优势,利用最小二乘法拟合可反演出准实时的E_10.7指数,均方根误差为5.445 sfu。利用高阶自回归模型对E_10.7的中期预报效果尚佳,未来27天的预报值平均相对误差为7.83%。利用同样方法还开展了E_10.7指数81天中心滑动平均值未来27天预报试验,未来27天的预报值平均相对误差仅为3.63%。      

多舱段载人航天器CO2去除系统性能仿真分析

多舱段载人航天器通常由主控舱段利用舱间通风对组合体空气环境参数进行集中控制.利用Ecosimpro建立了一种多舱段载人航天器CO₂去除系统性能仿真分析模型,包括舱体模块、乘员模块、CO₂净化模块、舱间通风模块,并对三舱段载人航天器CO₂去除系统性能进行了计算分析.结果表明,当净化装置进风量为0.007 2 kg/s,非主控舱段驻留人数达到6人时,会造成非主控舱段CO₂分压超出700 Pa的指标上限.此时增大舱间通风量对降低非主控舱段CO₂分压的效果并不明显,有效的控制方式是增大净化装置进风量.当净化装置进风量增加至0.011 3 kg/s时,非主控舱段CO₂分压可降至700 Pa以下.该工作有助于加快载人航天器空气环境控制系统的设计和改进流程.     

多级次孔结构ZnMn2O4微球负极的研究

利用水热法合成了Zn-Mn氧化物前驱体,在温度400、500、600、700℃下,空气气氛中煅烧前驱体,以此来制备纳米片组装成的分级多孔结构的ZnMn₂O₄微球。其中,在500℃空气中煅烧前驱体制备的ZnMn₂O₄（ZMO-500）微球具有丰富的多级次孔结构,其作为锂离子电池负极材料,在500 mA/g的电流密度下,ZMO-500微球负极材料循环500次以后仍具有1 132 mAh/g高的放电比容量。ZMO-500负极材料优异的电化学性能得益于其分级多孔结构,不仅可以增加电极和电解质之间的接触面积以促进锂离子的迁移,而且还为循环过程中电极体积膨胀提供足够的缓冲空间。      

Submillimeter spectroscopy from space — Missions planned between 1995 and 2005

The submillimeter wavelength range (100 μm ≤ λ ≤ 1 mm) is exceptionally rich in atomic and molecular transitions that provide direct measures of the chemical composition, temperature, density, and cooling of the interstellar medium. In part, this is due to the fact that the most abundant oxygen- and carbon-bearing species as well as the most common hydrides have their lowest lying transitions within this wavelength region. However, because of the great abundance of many of these same species in our own atmosphere (e.g., H₂O and O₂), terrestrial absorption at submillimeter wavelengths is strong, rendering much of the sky inaccessible to ground- and even airborne observing platforms. In recognition of the scientific importance of the submillimeter range to astronomy and the limitations placed on its pursuit by the atmosphere, both NASA and ESA have embarked on ambitious programs to explore these wavelengths from space.     

受控生态生保系统内红萍供氧特性研究

研究红萍载人供O₂特征, 为红萍生物部件进行系统总体地面模拟试验及空间应用奠定基础,构建了受控生态生保系统密闭试验舱和红萍栽培装置, 在“红萍-鱼-人”共存情况下, 测定密闭舱内O₂, CO₂浓度的变化. 试验结果显示, 单位重量的鱼耗O₂量. 0805～0.0831 L·kg-1·h-1, 排放CO₂量为0.0705～0.0736 L·kg-1·h-1; 试验志愿者耗O₂量19.71 L·h-1, 呼吸释放CO₂量18.90 L·h-1. 人工光照保持7000～8000 lx条件下, 红萍的光合作用与人和鱼的呼吸作用相辅相成, 舱内O₂, CO₂浓度趋于平衡. 密闭舱内CO₂浓度升高对促进红萍群体净光合效率有明显效果, 红萍光合放O₂能力很强, 能有效促使密闭舱内O₂, CO₂浓度朝着有利于人生存的环境方向平衡, 进而验证了红萍的空间应用前景.      

Organic molecules in the gas phase of dense interstellar clouds.

Since a previous COSPAR review on this subject, the number of molecular species identified by astronomers in dense interstellar clouds or in the envelopes expelled by evolved stars has grown from about eighty to approximately one hundred. Recent detections in stellar envelopes include the radical CP, the second phosphorus-containing astronomical molecule; SiN, the first astronomical molecule with a Si-N bond; and the HCCN radical. In the dense interstellar clouds recent detections or verifications of previous possible identifications include the H3O+ ion, which is a critical intermediary in the production of H2O and O2; the CCO radical, which is isoelectronic with HCCN; the SO+ ion, which appears to be diagnostic of shock chemistry; two new isomers of cyanoacetylene, HCCNC and CCCNH; and the two cumulenes H2C3 and H2C4. Some recent work is also described on the mapping of interstellar clouds in multiple molecular transitions in order to separate variations in chemical abundance from gradients in physical parameters.     

双通道辐射量计算太阳极紫外辐射E10.7指数方法初探

从太阳极紫外辐射研究的重要性出发, 介绍了太阳极紫外辐射E_10.7指 数及其作用, 详细阐述了利用两个能道的太阳辐射观测值计算极紫外辐射E_10.7指数的计算方法. 利用该方法对实测太阳辐射数据进行处理, 计算获得了2000-2005年的每日E_10.7指数, 并将计算结果 与Solar2000模式的输出结果进行对比分析, 验证了该计算方法的可行性, 对比结果表明, 最大相对误差在20%以内, 平均相对误差均在10%以内.      

卡尔曼滤波和自相关分析方法短期预报电离层f0F2的比较

电离层参数f₀F₂的预报是电离层研究的一个重要方向.本文选取2011年北京、长春、青岛和苏州四个常规观测站的f₀F₂数据,分别采用卡尔曼滤波、自相关分析法和国际参考电离层模型（IRI）对f₀F₂实施短期预报（提前1h预报）,并通过与实际观测数据的对比,对三种方法预报f₀F₂的性能进行了比较.研究结果表明,在磁平静时期,采用卡尔曼滤波方法进行f₀F₂预报的均方误差为0.532MHz,相对误差8.11%,比国际电离层参考模型的均方误差和相对误差分别降低1.47MHz和14.58%;采用自相关分析方法进行f₀F₂预报的均方根误差为0.967MHz,相对误差11.46%,比国际电离层参考模型的均方误差和相对误差分别降低1.035MHz和11.23%.比较结果说明二者对f₀F₂短期预报的精度相对于国际电离层参考模型均有大幅提升.对磁暴期间三种方法的预测性能做了进一步比较,试验结果表明卡尔曼滤波短期预报性能总体上优于自相关分析法,这为f₀F₂短期预报的方法选择提供了一定指导.      

Production and evolution of carbonaceous material by ion irradiation in space.

We review recent experimental studies concerning the evolution, driven by ion irradiation, of carbonaceous material from frozen gas to a refractory molecular solid. Under further irradiation the latter changes to a polymer-like material and ultimately to amorphous carbon. Most of the results have been obtained by "in situ" and remote IR and Raman spectroscopy. The results have been applied to demonstrate that molecular solids may be easily formed by irradiation of frozen mantles in dense interstellar clouds. Polymer-like material and amorphous carbons may result by further irradiation of organic mantles on grains in the diffuse interstellar medium. Those grains, during the aggregation to form extended bodies like comets (T-Tau phase of the Sun), are further modified. These latter are also irradiated, after the comet formation, during their long stay in the Oort cloud. In particular it has been suggested that comet may develop an ion-produced cometary organic crust that laboratory evidences show to be stable against temperature increases experienced during passages near the Sun. The comparison between the Raman spectra of some IDP (Interplanetary Dust Particles) and the Raman spectra of some ion-produced amorphous carbons, is also discussed.