Solid organic matter in the atmosphere and on the surface of outer Solar System bodies.

Many bodies in the outer Solar System display the presence of low albedo materials. These materials, evident on the surface of asteroids, comets, Kuiper Belt objects and their intermediate evolutionary step, Centaurs, are related to macromolecular carbon bearing materials such as polycyclic aromatic hydrocarbons and organic materials such as methanol and related light hydrocarbons, embedded in a dark, refractory, photoprocessed matrix. Many planetary rings and satellites around the outer gaseous planets display such component materials. One example, Saturn's largest satellite, Titan, whose atmosphere is comprised of around 90% molecular nitrogen N2 and less than 10% methane CH4, displays this kind of low reflectivity material in its atmospheric haze. These materials were first recorded during the Voyager 1 and 2 flybys of Titan and showed up as an optically thick pinkish orange haze layer. These materials are broadly classified into a chemical group whose laboratory analogs are termed "tholins", after the Greek word for "muddy". Their analogs are produced in the laboratory via the irradiation of gas mixtures and ice mixtures by radiation simulating Solar ultraviolet (UV) photons or keV charged particles simulating particles trapped in Saturn's magnetosphere. Fair analogs of Titan tholin are produced by bombarding a 9:1 mixture of N2:CH4 with charged particles and its match to observations of both the spectrum and scattering properties of the Titan haze is very good over a wide range of wavelengths. In this paper, we describe the historical background of laboratory research on this kind of organic matter and how our laboratory investigations of Titan tholin compare. We comment on the probable existence of polycyclic aromatic hydrocarbons in the Titan Haze and how biological and nonbiological racemic amino acids produced from the acid hydrolysis of Titan tholins make these complex organic compounds prime candidates in the evolution of terrestrial life and extraterrestrial life in our own Solar System and beyond. Finally, we also compare the spectrum and scattering properties of our resulting tholin mixtures with those observed on Centaur 5145 Pholus and the dark hemisphere of Saturn's satellite Iapetus in order to demonstrate the widespread distribution of similar organics throughout the Solar System.     

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.     

Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature.

Many experiments have already been carried out to simulate organic chemistry on Titan, the largest satellite of Saturn. They can provide fruitful information on the nature of minor organic constituents likely to be present in Titan's atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one already detected in Titan's atmosphere have been identified in simulation experiments. The exception, C4N2, as well as other compounds expected in Titan from theoretical modeling, such as other N-organics, and polyynes, first of all C6H2, have never been detected in experimental simulation thus far. All these compounds are thermally unstable, and the temperature conditions used during the simulation experiments were not appropriate. We have recently started a new program of simulation experiments with temperature conditions close to that of Titan's environment. It also uses dedicated analytical techniques and procedures compatible with the analysis of organics only stable at low temperatures, as well solid products of low stability in the presence of O2 and H2O. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range 100-150 K. Products were analysed by FTIR, GC and GC-MS techniques. GC-peaks were identified by their mass spectrum, and, in most cases, by comparison of the retention time and mass spectrum with standard ones. We report here the first detection in Titan simulation experiments of C6H2 and HC5N. Their abundance is a few percent relative to C4H2 and HC3N, respectively. Preliminary data on the solid products indicate an elemental composition corresponding to (H11C11N)n. These results open new prospects in the modeling of Titan's haze making.     

Analytical pyrolysis experiments of Titan aerosol analogues in preparation for the Cassini Huygens mission.

Comparative pyrolysis mass spectrometric data of Titan aerosol analogues, called "tholins", are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the interpretation of Titan atmosphere data from the Huygens probe in the future.     

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.     

Microbial life at extremely low nutrient levels

Many microorganisms (“oligotrophs”) grow in distilled water: spp., spp., spp., spp., spp., , spp., ( ) , spp., yeasts, and spp. Also, certain lower fungi can be found here. In the laboratory, these organisms thrive on contaminations of the air (CO, hydrocarbons, H₂, alcohols etc.). All are euryosmotic and often grow also in higher concentrations of salts and nutrients. Natural locations with extremely low nutrient levels (snow, rain water pools, springs, free ocean water, Antarctic rocks and soils) do not contain more than 1–5 mg/1 of organic carbon. Oligotrophs found here are especially adapted to constant famine: they frequently live attached to surfaces, form polymers and storage products even while starving, and often aggregate. Many of these oligotrophs alter their morphology (surface to volume ratio) with changing nutrient concentrations. Extreme oligotrophs also occur in generally nutrient-rich environments such as sewage aeration tanks or compost soil. Here they are thought to survive in nutrient-depauperate microhabitats.     

Towards validation of SCIAMACHY lunar occultation NO2 vertical profiles

Vertical profiles of stratospheric nitrogen dioxide (NO₂) have been retrieved from moderate resolution lunar occultation transmission spectra measured by Scanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY) on board the European Environmental Satellite (ENVISAT). These measurements were taken over the high southern latitude of 50°–90° during the period of 2003–2005. To assess the accuracy of the retrieved NO₂ profiles, the SCIAMACHY nighttime NO₂ profiles were compared with NO₂ profiles retrieved from sunrise solar occultation spectra measured by the Halogen Occultation Experiment (HALOE) and the Stratospheric Aerosol and Gas Experiments II (SAGE II) using a photochemical correction model. The validation results show good agreement of SCIAMACHY lunar occultation NO₂ with scaled HALOE and SAGE II profiles. The relative mean differences (rmd) with scaled HALOE profiles are within −13% to +5% and standard deviations (rms) of the relative differences are within 3–19% between 25 and 38 km. The rmd and rms with scaled SAGE II NO₂ profiles are in the range of −9 to +7 and 10–17% respectively between 22 and 39 km.     

The GPS measured SITEC caused by the very intense solar flare on July 14, 2000

This work studies the sudden increases in total electron content of the ionosphere caused by the very intense solar flare on July 14, 2000. Total electron content (TEC) data observed from a Global Positioning System (GPS) network are used to calculate the flare-induced TEC increment, δTEC_f, and variation rate, dTEC_f/dt. It is found that both dTEC_f/dt and δTEC_f are closely related with the solar zenith angles. To explain the observation results, we derived a simple relationship between the partial derivative of the flare-induced TEC, ∂TEC_f/∂t, which is a good approximation for dTEC_f/dt, and the solar zenith angle χ, as well as the effective flare radiation flux I_f, according to the well-known Chapman theory of ionization. The derived formula predicted that ∂TEC_f/∂t is proportional to I_f and inverse proportional to Chapman function ch(χ). This theoretical prediction not only explains the correlation of dTEC_f/dt and δTEC_f with χ as shown in our TEC observation, but also gives a way to deduce I_f from TEC observation of GPS network. Thus, the present work shows that GPS observation is a powerful tool in the observation and investigation of solar flare effects on the ionosphere, i.e., the sudden ionospheric disturbances, which is a significant phenomenon of space weather.     

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.     

Formation of bioorganic compounds in simulated planetary atmospheres by high energy particles or photons.

Various types of organic compounds have been detected in Jupiter, Titan, and cometary coma. It is probable that organic compounds were formed in primitive Earth and Mars atmospheres. Cosmic rays and solar UV are believed to be two major energy sources for organic formation in space. We examined energetics of organic formation in simulated planetary atmospheres. Gas mixtures including a C-source (carbon monoxide or methane) and a N-source (nitrogen or ammonia) was irradiated with the followings: High energy protons or electrons from accelerators, gamma-rays from 60Co, UV light from a deuterium lamp, and soft X-rays or UV light from an electron synchrotron. Amino acids were detected in the products of particles, gamma-rays and soft X-rays irradiation from each gas mixture examined. UV light gave, however, no amino acid precursors in the gas mixture of carbon monoxide, nitrogen and nitrogen. It gave only a trace of them in the gas mixture of carbon monoxide, ammonia and water or that of methane, nitrogen and water. Yield of amino acid precursors by photons greatly depended on their wavelength. These results suggest that nitrogen-containing organic compounds like amino acid precursors were formed chiefly with high energy particles, not UV photons, in Titan or primitive Earth/Mars atmospheres where ammonia is not available as a predominant N-source.     

等离子体对燃气在补燃室中燃烧特性的影响

为研究等离子体对多组分燃气在发动机补燃室中的助燃特性,建立了多组分燃气供给系统以及扩散燃烧实验模型。测量了等离子体炬的发射光谱,得到了等离子体炬的主要激发态粒子;拍摄了多组分燃气在补燃室的扩散火焰照片,得到了等离子体对多组分燃气的扩散火焰形貌的影响;测量了补燃室4个不同截面上的静压和总压,分析了等离子体对多组分燃气在发动机中燃烧效率的影响。实验结果表明:等离子体炬主要产生氮气和氧气的激发态粒子;加入等离子体后,喷出冲压尾喷管的火焰长度得到进一步缩短,说明等离子体可以在更短的燃烧室长度内使得多组分燃气得到更加充分的燃烧;加入等离子体时,补燃室不同截面的静压和总压都会出现突升台阶,说明等离子体可以加快燃气的化学反应速率,提高多组分燃气在发动机中的燃烧效率,且等离子体功率越高,燃气燃烧效率的增长率越高。     

Biological modulation of the terrestrial carbon cycle: Isotope clues to early organic evolution

The characteristic difference of some 20 to 30 ‰ in the ¹³C/¹²C rations of reduced (organic) and oxidized (carbonate) carbon as observed in the contemporary environment can be traced back over 3.5 (if not 3.8) Ga of recorded Earth history. There is little doubt that the enrichment of isotopically light carbon in fossil organic matter ultimately derives from the bias in favor of ¹²C during photosynthetic carbon fixation (notably the RuBP carboxylase reaction of the Calvin cycle). Accordingly, the mainstream of the sedimentary δ ¹³C_org record can be most reasonably explained as geochemical evidence of the isotope-discriminating properties of the principal CO₂-fixing enzymatic reaction of the assimilatory pathway, thus giving eloquent testimony to an extreme degree of evolutionary conservatism in the biochemistry of autotrophic carbon fixation.     

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.     

Intensity profiles of the multiple scattering light near the cometary nucleus

The multiple scattering of solar radiation in the cometary atmosphere is treated with the method of successive scattering. Referring to in situ measurements of comet Halley about the size and spatial distributions of dust, the optical thickness τ₁ of dust has been estimated, i.e. τ₁=0.03 at wavelength λ=0.62μm in a quiet time, but τ₁=0.3 when the outbursts/jets occur. In the derivation of τ₁, optical properties of dust including a mixing ratio of absorbing to silicate grains, are determined based on the polarimetry of P/Halley at λ=0.62μm observed during the phase angles over Nov. 1985 to May 1986 at the Dodaira Station of Tokyo Astronomical Observatory.

It is found that a temporary enhancement of τ₁ leads an increase of the upward reflected intensity when the surface albedo A of the nucleus is less than 0.04, but the reverse is true when A>0.04. On the other hand, the intensity of the downward radiation at the surface of the nucleus always decreases as an increase of τ₁.     

一种高压孔板气体大流量校准技术研究

建立一种高压孔板气体大流量校准装置,解决了增压输送系统高压孔板流量系数计量难题。该装置可实现最高压力30MPa,最大质量流量18000kg/h（氮气）的气体流量检测,不确定度为0.5%（k=2）。     

Diagnosing the storm-time ring current and other magnetospheric plasma domains using relativistic electron data

Ring current ions and relativistic electrons simultaneously measured on board MOLNIYA-1 are analyzed in comparison with the ground-based magnetometer data for the period of a strong magnetic storm (|D_st|max≈230 nT). Injection of >500 keV electrons into the slot region (L≈3) near equatorial plane is occurred on time scale ≈1 hour, when, during the magnetic storm maximum, the extreme low-latitude position of auroral electrojets is reached and ring current becomes more symmetrical. Positions of both the ring current maximum and electron intensity maximum (L_max) are consistent to our previous result: |D_st|_max = 2.75 • 10⁴/L⁴_max. An extreme storm-time low-latitude position of the west electrojet center (for amplitudes of |D_st|_max up to 600 nT) is shown to be in a good consistence with this empirical dependence. It is supposed the trapped radiation boundary collapses down to L≈L_max in the course of the storm main phase.     

The dark matter halo structure of “fossil” groups candidates

We investigated properties of four isolated giant elliptical galaxies with extended X-ray halo using ASCA data. The derived size of X-ray halo, X-ray luminosity, and gravitational mass of the dark halo are unusually large those of X-ray halo of a single galaxy, but are typical for X-ray halos of groups and poor clusters of galaxies. The measured temperatures and abundances of the X-ray halo gas in these galaxies are also similar to those of the groups and poor clusters. Based on these results we identified these galaxies as “isolated X-ray overluminous elliptical galaxy” (IOLEG). The radial profiles of dark halo in these objects were derived from X-ray data. It is found that some are similar to those of compact groups while others are the same as those of normal ellipticals. The dark halos of lOLEGs are thus indistinguishable from those of groups (and poor clusters), which appears to be consistent with a widely believed idea that lOLEGs are a product of dynamical evolution of a compact group. However, mass-to-light ratios of IOLEGs (M₂₀₀/L_B  100–1000) are far greater than those of Hickson compact groups M₂₀₀/L_B  40–60). Since it is hard to consider that total optical luminosity of a compact group decreases by an order of magnitude in the course of dynamical evolution, such difference in the observed mass-to-light ratio between IOLEGs and Hickson compact groups strongly suggests that most IOLEGs have not evolved from compact groups which are observed at present.     

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.     

Numerical simulations of the radiance from the comet 46P/Wirtanen in the various configurations of the measurements during “Rosetta” mission

The work we present deals with the spectrometric measurements of VIRTIS instrument of the Comet P/Wirtanen planned for the Rosetta mission. This spectrometer can monitor (VIRTIS M channel: 0.250μm – 0.980μm; Δκ=20cm⁻¹; 0.980 – 5.0 μm; Δκ = 5cm⁻¹; VIRTIS H channel: 2.0 μm – 5.0 μm; Δκ=2cm⁻¹) the nucleus and the coma in order to provide a general picture of coma's composition, the production of gas and dust, the relationship of coma production to surface composition and the structure and variation of mineralogy of the nucleus surface. During the mission the observation conditions of the spectroscopic investigation change due to different relative positions spacecraft/comet, and to the different illumination conditions of the surface at various distances of the comet to the Sun. The nucleus surface is continuously modified by the ice sublimation accompanied by gas and dust emission. Consequently the surface also its spectrophotometric properties changes and their monitoring can give a new insight. The important role of simulations is to predict the results of measurements in various experimental condition what, in the future, can help in interpretation of the measured data.

In this paper the first results of our simulation the radiance from the comet in the 0.25–5.0μm spectral range at two distances from the Sun (1AU and 3AU) are shown. The distance between the Rosetta orbiter and the nucleus surface as well as the sun zenith angles are taken into account according to the Rosetta mission phases. In fact the surface and coma properties vary along the comet orbit, and should be taken into account in our calculations. The optical parameters of the dust on the surface (e.g. reflectance) and in the coma (e.g. Q_ext) were calculated from optical constants of possible comet analogues. The thermodynamic parameters of the comet are taken from the models of comet evolution. Through this kind of modelling it is possible to identify the surface characteristics in spectra of the radiation from the surface of nucleus transmitted through the coma loaded with dust and gases.

Even if the “Rosetta mission” is postponed, with the consequence of a target change, we think that our idea and the method used for the simulations can be useful also for the new Rosetta target - the comet 67P/Churyumov Gerasimenko.     

释放SF6气体扰动电离层时的人工气辉研究

在电离层高度释放SF₆气体能够显著扰动电离层.根据SF₆分子在电离层中的扩散方程,同时考虑其在电离层中主要的离子化学反应,研究了SF₆气体释放后电离层各粒子浓度的时空变化,计算了产生人工气辉的体发射系数和发射强度.结果表明,SF₆气体在电离层高度释放后,电子和O⁺的密度均有大幅度下降,主要的负离子成分由电子转变成SF₅^-;在释放过程中,主要产生777.4 nm和135.6 nm两种气辉,且前者的气辉强度远小于后者;电离层温度对气辉的强度有很大的影响.本文的数值计算与美国IMS/SF₆实验观测数据进行比较,结果近似,且通过数据比较还能准确推断出实验时当地的电离层温度.