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.     

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.     

Remote infrared observations of parent volatiles in comets: A window on the early solar system

Organic volatiles and water in Oort Cloud comets were investigated at infrared wavelengths. The detected species include H₂O, CO, CH₃OH, CH₄, C₂H₂, C₂H₆, OCS, HCN, NH₃, and H₂CO. Several daughter fragments (CN, OH, NH₂, etc.) are also measured, and OH prompt emission provides a proxy for water. Long-slit spectra are taken at high spectral dispersion and high spatial resolution, eliminating several sources of systematic error. The resulting parent volatile production rates are highly robust, permitting a sensitive search for compositional diversity among comets. Here, seven OC comets are compared. Six (including Halley) exhibit similar compositions (excepting CO and CH₄). Their low formation temperatures (30 K) suggest this group probably formed beyond 30 AU from the young sun. However, C/1999 S4 is severely depleted in hypervolatiles and also in methanol, and it likely formed near 5–10 AU. C/2001 A2 is discussed briefly to illustrate future prospects.     

太赫兹火星大气临边探测仿真研究

对火星大气进行连续高分辨率观测是研究火星大气物理和化学过程的重要手段.太赫兹临边探测技术通过测量火星大气中的风和光化学循环中的重要气体（CO，O₃，H₂O，H₂O₂等）提高对火星的认知.针对火星大气遥感的探测需求，分析了300～1000GHz频段的频谱特征.针对探测卫星对于载荷质量、功耗等参数的要求，提出一个560GHz频段的火星大气太赫兹临边探测仪设计方案，并利用辐射传输模型ARTS中的行星工具箱进行仿真.仿真结果显示:火星大气温度的反演精度优于4K，其中45km高度以下优于2K；H₂O丰度的反演精度在90km以下优于50%，30km以下优于2%；H₂O₂的反演精度在40km以下优于50%；O₃的反演精度在50km以下优于60%；大气风速度的反演精度在65km以上优于5m·s-1，最高可以达到2m·s-1.研究结果表明，利用太赫兹波段的吸收谱线可以很好地探测火星大气中各成分的丰度、变化趋势以及中高层大气的风，可为后续火星表面及大气探测提供参考.      

密闭空间内氢气和二氧化碳甲醇化系统的非均相模型及反应特性

在载人密闭空间内通过电解水方式为乘员供氧会产生副产物氢气（H₂）。此外,乘员还呼出二氧化碳（CO₂）。将H₂和CO₂催化合成甲醇（CH₃OH）是消除载人密闭空间内富余H₂和CO₂的最优方式之一。对其开展反应过程建模及反应特性研究有助于进行反应过程的控制,更好地维持载人密闭空间内的大气平衡。本文采用微元法建立了H₂和CO₂催化合成甲醇的物料计算模型和温度一维非均相模型,研究了不同反应压力、冷却介质温度以及入口反应气体中CO₂与CO比值等反应条件下的反应特性变化规律。结果显示,反应压力的增加、冷却介质的温升以及入口气体中CO₂与CO比值的减小均能促进各反应速率增加,进而使得H₂和CO₂消除量增加、甲醇合成率上升以及催化剂和反应气体最高温度上升。在保证反应速率增加且催化剂最高温度不超过合理反应温度区间的最大值573.15 K时需维持反应压力不大于8 MPa,冷却介质温度不高于538.15 K以及CO₂与CO比值不小于1。      

The search for nitrogen compounds on the surface of Mars

Nitrogen is an essential element for life. Specifically, “fixed nitrogen” (i.e., NH₃, NH₄⁺, NO_x, or N that is chemically bound to either inorganic or organic molecules and is releasable by hydrolysis to NH₃ or NH₄⁺) is the form of nitrogen useful to living organisms. To date no direct analysis of Martian soil nitrogen content, or content of fixed nitrogen compounds has been done. Consequently, the planet's total inventory of nitrogen is unknown. What is known is that the N₂ content of the present-day Martian atmosphere is 0.2 mbar. It has been hypothesized that early in Mars' history (3 to 4 billion years ago) the Martian atmosphere contained much more N₂ than it does today. The values of N₂ proposed for this early Martian atmosphere, however, are not well constrained and range from 3 to 300 mbar of N₂. If the early atmosphere of Mars did contain much more N₂ than it does today the question to be answered is, Where did it go? The two main processes that could have removed it rapidly from the atmosphere include: 1) nonthermal escape of N-atoms to space; and 2) burial within the regolith as nitrates and nitrites. Nitrate will be stable in the highly oxidized surface soil of Mars, and will tend to accumulate in the soil. Such accumulations are observed in certain desert environments on Earth. Some NH₄⁺---N may also be fixed and stabilized in the soil by inclusion as a structural cation in the crystal lattices of certain phyllosilicates replacing K. Analysis of the Martian soil for traces of NO₃⁻ and NH₄⁺ during future missions will supply important information regarding the nitrogen abundance on Mars, its past climate as well as its potential for the evolution of life.     

火星大气模型参数对MSL气动特性的影响

火星大气与地球大气截然不同,飞行器在进入火星时气动特性不同于地球再入. 大气模型的差异主要表现为气体组份、密度和温度等物理参数. 针对火星进入器MSL在进入-下降-着陆过程中的高超声速进入段,利用三维并行程序求解耦合真实气体模型的流体动力学Navier-Stokes方程,分析MSL进入火星大气时大气模型参数对进入器气动特性的影响. 结果表明,通过与海盗号飞行数据的对比,验证了所采用的火星气体模型和计算方法,且其与NASA的 LAURA代码气动特性计算结果也较为一致;大气模型气体性质,即CO₂环境对进入器阻力系数和俯仰力矩系数影响较大,利用空气得到的计算和实验数据必须考虑CO₂效应;密度增大促进了化学非平衡效应,但对进入器气动特性基本没有影响;温度升高大大增强了化学非平衡效应,而对进入器气动特性影响较小.      

H2O对空间站5A分子筛CO2去除性能影响

为进一步研究分子筛CO2去除系统应用于空间站的工作可靠性和鲁棒性,针对空间站4床分子筛(4-BMS)系统中可能出现的湿度失效保护问题展开了实验研究.测试了两种载人航天分子筛材料TC-5A与PSA-5A,研究了不同相对湿度对CO2吸附性能的影响;比较了相同湿度条件下,进口气体CO2浓度、粒径及吸附温度的变化对分子筛吸附CO2性能的影响,采用不同实验方法探究了H2O和CO2在两种分子筛材料中的竞争吸附关系.结果表明:PSA-5A吸附CO2性能优于TC-5A,但对H2O的吸附率略低于TC-5A.H2O的存在对分子筛吸附CO2影响非常大,空气中相对湿度达到60%时,分子筛基本失去了吸附CO2的能力.此外,温度升高会造成CO2的吸附量显著下降,但对H2O的吸附量影响相对较小,尤其是当相对湿度较高时.这对中国未来长期运行的空间站分子筛CO2去除系统工作有效性与工作鲁棒性的评价具有指导意义.     

Photochemistry of planetary ionospheres

The basic photochemical processes in the upper atmospheres and ionospheres of the various bodies in our solar system (planets, moons and comets) are similar. However, there are many different factors (e.g. gas composition, energy input, gravity) which control/change the relative importance of these controlling processes. The photo-chemistry of the inner planets is reasonably well understood at this time, thus there is good agreement between model calculations and most of the observational data base. The extremely limited information that we have available on the ionospheres of the outer planets leads to significant uncertainties about some of the controlling processes. Some important questions (e.g. Is the charge exchange process H⁺ + H₂(v≥4) → H₂⁺ + H important? Is water vapor influx from the rings important?) remain unanswered at this time. In cometary atmospheres the freshly evaporated parent molecules are rapidly photodissociated and photoionized, therefore most of the chemical kinetics of cometary ionospheres involve these rapidly moving and highly reactive ions and radicals.     

Neutral upper atmospheres of Venus and Mars

Numerous measurements of the neutral upper atmosphere above 100 km have been made from spacecraft over Venus and over Mars. The Venus exospheric temperatures are unexpectedly low (less than 300°K near noon and less than 130°K near midnight). These very low temperatures may be partially caused by collisional excitation of CO₂ vibrational states by atomic oxygen and partially by eddy cooling. The Venus atmosphere is unexpectedly insensitive to solar EUV variability. On the other hand, the Martian dayside exospheric temperature varies from 150°K to 400°K over the 11-year solar cycle, where CO₂ 15-μm cooling may be less effective because of lower atomic oxygen mixing ratios. On Venus, temperature increases with altitude on the dayside (thermosphere), but decreases with altitude from 100 to 150 km on the nightside (cryosphere). However, dayside Martian temperatures near solar minimum for maximum planet-sun distance and low solar activity are essentially isothermal from 40 km to 200 km. During high solar activity, the thermospheric temperatures of Mars sharply increase. The Venus neutral upper atmosphere contains CO₂, O, CO, C, N₂, N, He, H, D and hot nonthermal H, O, C, and N, while the dayside Mars neutral upper atmosphere contains CO₂, O, O₂, CO, C, N₂, He, H, and Ar. There is evidence on Venus for inhibited day-to-night transport as well as superrotation of the upper atmosphere. Both atmospheres have substantial wave activity. Various theoretical models used to interpret the planetary atmospheric data are discussed.     

释放不同化学物质对电离层扰动的比较

在电离层F区释放氢（H₂）、水（H₂O）、二氧化碳（CO₂）、六氟化硫（SF₆）、三氟溴甲烷（CF₃Br）、羰基镍（Ni（CO）₄）可以损耗局域等离子体电子密度,形成电子空洞,电离层电子密度的改变主要取决于释放物质的气态分子与电离层之间的离子化学反应.在电离层人工主动扰动实验中,应根据发射成本和扰动效果对释放物质进行选择.通过热力学原理和有限元模拟方法计算比较了上述6种物质对电离层的扰动影响.计算结果表明,6种物质中水的气化率最低,约为19%,其余5种物质都在60%以上,选择密度小的物质,例如H₂和CO₂,可以有效降低发射成本.另外,扩散较慢且化学反应较快的物质,例如SF₆和Ni（CO）₄,能够使得电离层电子密度减少得更多,并且受扰动区域更广、持续时间更长.     

Cometary atmosphere (gas and dust)

There is important progress now in the identifications and measurements of primary (parent) molecules in the inner coma of Comet Halley. H₂O, CO₂ and CO are definitely in the list, CH and some complicate organic molecules are suspected. Gas production rate for water vapor is Q_H2O 10³⁰ s⁻¹. The bulk of data doesn't contradict to the Whipple model of nucleus (with clathrate modification). Pronounced spatial structure of gaseous flow in the coma was observed, but in general measured properties of neutral gas in the coma of Comet Halley are not very different from predicted. Situation for dust is different. In situ dust measurements show that size spectrum and optical properties of particles in coma are substantively declining from predicted on the base of groundbased photometry. However there are discrepancies between Vega and Giotto dust counter data. Dust in the inner coma didn't prevent the succesful imaging of nucleus by TV on Vega 1 and 2.     

Search for methane on Mars: Observations,interpretation and future work

The detection of methane on Mars has been reported by three different teams in 2004. Two of them used ground-based high-resolution spectroscopy in the near infrared range. The third one used the Planetary Fourier Spectrometer aboard Mars Express. Among the data sets, two of them reported a mean CH₄ mixing ratio of 10 ppb. However, these are marginal detections, which should be considered as tentative. The third (ground-based) data set, unpublished so far, seems to show evidence for strong localized sources of CH₄, corresponding to mixing ratios as high as 250 ppb in some cases. However, the high values reported in 2003 were not confirmed by subsequent observations performed by the PFS instrument in 2004. In the absence of a refereed publication, it is difficult to judge if the high values are indeed correct. Assuming that they are, the lack of their confirmation by the PFS could have several explanations, including, among others, localized transient vents, or time variations in the methane destruction rate. A biogenic source was first suggested for the martian methane. However, later studies showed that an abiotic source such as hydrogeology can be just as effective. Further dedicated observations are obviously needed to firm up the detection and distribution of methane on Mars.     

The 2.5 to 5 microns spectrum of comet Halley from the IKS instrument of Vega

Results of the 2.5–5 micron spectroscopic channel of the IKS instrument on Vega are reported and the data reduction process is described. H₂O and CO₂ molecules have been detected with production rates of 10³⁰ s⁻¹ and 1.5 10²⁸ s⁻¹ respectively. Emission features between 3.3 and 3.7 microns are tentatively attributed to CH - bearing compounds - CO is marginally detected with a mixing ratio CO/H₂O 0.2. OH emission and H₂O - ice absorption might also be present in the spectra.     

Did life exist on Mars? Search for organic and inorganic signatures, one of the goals for “SAM” (sample analysis at Mars)

Observation of Mars shows signs of a past Earth-like climate, and, in that case, there is no objection to the possible development of life, in the underground or at the surface, as in the terrestrial primitive biosphere. Sample analysis at Mars (SAM) is an experiment which may be proposed for atmospheric, ground and underground in situ measurements. One of its goals is to bring direct or indirect information on the possibility for life to have developed on Mars, and to detect traces of past or present biological activity. With this aim, it focuses on the detection of organic molecules: volatile organics are extracted from the sample by simple heating, whereas refractory molecules are made analyzable (i.e. volatile), using derivatization technique or fragmentation by pyrolysis. Gaseous mixtures thus obtained are analyzed by gas chromatography associated to mass spectrometry. Beyond organics, carbonates and other salts are associated to the dense and moist atmosphere necessary to the development of life, and might have formed and accumulated in some places on Mars. They represent another target for SAM. Heating of the samples allows the analysis of structural gases of these minerals (CO₂ from carbonates, etc.), enabling to identify them. We also show, in this paper, that it may be possible to discriminate between abiotic minerals, and minerals (shells, etc.) created by living organisms.     

VEGA three-channel spectrometer experiment: Spectroscopy of comet Halley in the visible and near-ultraviolet ranges

A total of 3600 spectra of Comet Halley in the 275–710 nm were obtained on March, 8, 9, 10 and 11, 1986, from the VEGA 2 spacecraft. The emissions of OH, NH, CN, C₃, CH, C₂, NH₂ and H₂O⁺ are identified. From the OH intensity in the (0,0) band: 1.1 Megarayleigh at 5400 km from the nucleus, it can be inferred that the OH production rate was (1.4 ± 0.5)×10³⁰ molecules s⁻¹. The NH, C₃, CH and NH₂ bands became comparatively more intense at distances from the nucleus shorter than 3000km. At 06:40 U.T. when the instrument field of view was 6000×4500 km, two jets were observed. Spectra from the jets show significant differences with other spectra. Inside a jet NH, C₃ and NH₂ are comparatively more intense and the rotational distributions of OH, CN and C₂ are strongly distorted. This shows that part of the observed emissions probably comes from radicals directly produced in the excited state during the initial process of photolysis of the parent molecules.     

Survival and death of the haloarchaeon Natronorubrum strain HG-1 in a simulated martian environment

Halophilic archaea are of interest to astrobiology due to their survival capabilities in desiccated and high salt environments. The detection of remnants of salty pools on Mars stimulated investigations into the response of haloarchaea to martian conditions. Natronorubrum sp. strain HG-1 is an extremely halophilic archaeon with unusual metabolic pathways, growing on acetate and stimulated by tetrathionate. We exposed Natronorubrum strain HG-1 to ultraviolet (UV) radiation, similar to levels currently prevalent on Mars. In addition, the effects of low temperature (4, −20, and −80 °C), desiccation, and exposure to a Mars soil analogue from the Atacama desert on the viability of Natronorubrum strain HG-1 cultures were investigated. The results show that Natronorubrum strain HG-1 cannot survive for more than several hours when exposed to UV radiation equivalent to that at the martian equator. Even when protected from UV radiation, viability is impaired by a combination of desiccation and low temperature. Desiccating Natronorubrum strain HG-1 cells when mixed with a Mars soil analogue impaired growth of the culture to below the detection limit. Overall, we conclude that Natronorubrum strain HG-1 cannot survive the environment currently present on Mars. Since other halophilic microorganisms were reported to survive simulated martian conditions, our results imply that survival capabilities are not necessarily shared between phylogenetically related species.     

Photochemical growing of complex organics in planetary atmospheres

UV induced syntheses of organic compounds from the main atmospheric constituents can be a very important source of organics in a given planetary environment provided the atmosphere is in a reduced state. The evolution of a CO₂ rich medium only produces very low yields of formaldehyde and related oxygenated compounds. Considering a CO rich atmosphere, the photochemical yield of O-organics formation is much higher, when the synthesis of N-organics remains difficult. The most favourable atmosphere as far as photochemical organic synthesis is concerned is a CH₄ rich milieu.. The photochemical evolution of such a CH₄ atmosphere under UV irradiation leads to a chain of various organics, the complexity of which increases together with the number of pathways involved in their formation. Their complexity also closely correlates with their UV photoabsorption spectrum: the more complex they are, the more shifted is their UV spectrum toward the visible range. Direct photodissociation of methane requires UV photon of wavelengths shorter than about 145 nm. It mainly produces ethane which absorbs UV at wavelengths shorter than about 160 nm, and acetylene, that presents an absorption spectrum extending up to 200 nm. This shift still continuously increases with further increase in number of C atoms. Unsaturated hydrocarbons with 4 and more C atoms have UV absorption characteristics including noticeable band structures in the 250–300 nm range. This trend has very important implication in the photochemical behaviour of a CH₄-rich planetary atmosphere, as it induces many catalytic processes. The occurrence of such processes is closely related to vertical atmospheric and energy deposition profiles. Titan provides a very good example of such a UV-directed organic atmospheric chemistry.     

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.