Atmospheric photochemistry above possible martian hot spots

Considering the possibility of outgassing from some localized sources on Mars, we have developed a one-dimensional photochemical model that includes methane (CH₄), sulfur dioxide (SO₂) and hydrogen sulfide (H₂S). Halogens were considered but were found to have no significant impact on the martian atmospheric chemistry. We find that the introduction of methane into the martian atmosphere results in the formation of mainly formaldehyde (CH₂O), methyl alcohol (CH₃OH) and ethane (C₂H₆), whereas the introduction of the sulfur species produces mainly sulfur monoxide (SO) and sulfuric acid (H₂SO₄). Depending upon the flux of the outgassed molecules from possible hot spots, some of these species and the resulting new molecules may be detectable locally, either by remote sensing (e.g., with the Planetary Fourier Spectrometer on Mars Express) or in situ measurements.     

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.      

Contribution of solar UV radiation to the observed ozone variations during the 21st and 22nd solar cycles

A two-dimensional dynamical radiative-photochemical model of the ozonosphere including aerosol physics is used to examine the changes of the Earth's ozone layer occurred during the 21st and 22nd solar cycles. The calculated global total ozone changes in the latitude range 60°S—60°N caused by 11-year variation of solar UV radiation, volcanic eruptions, and anthropogenic atmospheric pollution containing CO₂, CH₄, N₂O and chlorine and bromine species are in a rather good agreement with the observed global ozone trend. The calculations show that the anthropogenic pollution of the atmosphere is a main reason of the ozone depletion observed during the last two solar cycles. However, the 11-year solar UV variation as well as volcanic eruptions of El Chichon and Mt. Pinatubo also gave a significant contribution to the observed global ozone changes.     

New insights into Titan's organic chemistry in the gas and aerosol phases.

Titan, the largest satellite of Saturn, with a dense atmosphere very rich in organics, and many couplings in the various parts of its "geofluid", is a reference for studying prebiotic chemistry on a planetary scale. New data have been obtained from experiments simulating this organic chemistry (gas and aerosol phases), within the right ranges of temperature and a careful avoiding of any chemical contamination. They show a very good agreement with the observational data, demonstrating for the first time the formation of all the organic species already detected in Titan atmosphere including, at last, C4N2, together with many other species not yet detected in Titan. This strongly suggests the presence of more complex organics in Titan's atmosphere and surface, including high molecular weight polyynes and cyanopolyynes. The NASA-ESA Cassini-Huygens mission has been successfully launched in October 1997. The Cassini spacecraft will reach the Saturn system in 2004 and become an orbiter around Saturn, while the Huygens probe will penetrate into Titan's atmosphere. In situ measurements, in particular from Huygens GC-MS and ACP instruments, will provide a detailed analysis of the organics present in the air, aerosols, and surface. This very ambitious mission should yield much information of crucial importance for our knowledge of the complexity of Titan's chemistry, and, more generally for the field of exobiology.     

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.     

The organic aerosols of Titan

A dark reddish organic solid, called tholin, is synthesized from simulated Titanian atmospheres by irradiation with high energy electrons in a plasma discharge. The visible reflection spectrum of this tholin is found to be similar to that of high altitude aerosols responsible for the albedo and reddish color of Titan. The real (n) and imaginary (k) parts of the complex refractive index of thin films of Titan tholin prepared by continuous D.C. discharge through a 0.9 N₂/0.1 CH₄ gas mixture at 0.2 mb is determined from x-ray to microwave frequencies. Values of n (1.65) and k (0.004 to 0.08) in the visible are consistent with deductions made by ground-based and spaceborne observations of Titan. Many infrared absorption features are present in k(λ), including the 4.6 μm nitrile band. Molecular analysis of the volatile component of this tholin was performed by sequential and non-sequential pyrolytic gas chromatography/mass spectrometry. More than one hundred organic compounds are released; tentative identifications include saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. In addition, acid hydrolysis produces a racemic mixture of biological and non-biological amino acids. Many of these molecules are implicated in the origin of life on Earth, suggesting Titan as a contemporary laboratory environment for prebiological organic chemistry on a planetary scale.     

Organic syntheses in gas phase and chemical evolution in planetary atmospheres

Atmospheric chemistry may be one of the important pathways to the synthesis of organic compounds in a planetary periphery. Depending on the nature of the carbon source (CH₄, CO or CO₂), the main composition of the atmosphere, and the respective roles of the various energy sources, is it possible, and to what extent, to produce organics? What kind of gaseous mixture is the most favourable to prebiotic organic syntheses? How far can the results of laboratory works be extrapolated to the case of planetary atmospheres? These questions are discussed, on the basis of several available laboratory data, and by considering the main atmospheric composition of the planets of the solar system, and the list of organic compounds which have already been dettected in their atmospheres.     

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.     

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.     

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.     

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%。      

The escape of molecular hydrogen and the synthesis of organic nitriles in planetary atmospheres.

What is the influence of hydrogen escape from the atmosphere of small planetary bodies on the synthesis of organic molecules in that atmosphere? To answer this question, laboratory experiments have been performed to study the evolution of different reducing model atmospheres submitted to electrical discharges, with and without the simulation of H₂ escape. A study of mixtures of nitrogen and methane shows a very strong effect of H₂ escape on the formation of organic nitriles, the only nitrogen containing organics detected in the gas phase. These are HCN, CH  CCN, (CN)₂, CH₂CHCN, CH₃ CN and CH₃CH₂CN. The yield of synthesis of most of these compounds is noticeably increased, up to several orders of magnitude, when hydrogen escape is simulated. The escape of H₂ from the atmosphere of the primitive Earth may have played a crucial role in the formation of reactive organic molecules such as CHCCN or (CN)₂, which can be considered as important prebiotic precursors. These experimental results may also explain extant data concerning the nature and relative abundance of organics present in the atmosphere of Titan, a planetary satellite which may be an ideal model within our solar system for the study of organic cosmochemistry and exobiology.     

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.     

Absorbers seen near the Venus cloud tops from pioneer Venus

Spin-scan images from the Pioneer Venus Orbiter UV Spectrometer and the Cloud Photopolarimeter provide a set of planetary contrast measurements in the wavelength range 1990A to 3650A and phase angles from 33°–130°. The planet is darkest at the point where the UVS line of sight penetrates perpendicular to the cloud tops: thus the absorbing material responsible must be deep in the atmosphere. Sulfur dioxide absorption can explain the amount of contrast seen between 2000A and 3200A. At the longer wavelengths, the persistence of contrast requires another absorber which is deeper in the atmosphere and strongly associated with the location of the SO₂. Part of the observed contrast is due to the high-lying haze discovered from Pioneer Venus polarimetry. The correlation between planetary contrast and polarization does not support large scale clearing or major vertical motions of the cloud tops as the sole cause of the observed contrast. However, a scheme in which absorbers subject to photochemical destruction are mixed upward into the cloud top region provides a consistent explanation for the origin of these markings.     

Development of an extreme ultraviolet imaging spectrometer for the BepiColombo mission

Extreme and far ultraviolet imaging spectrometers are proposed for the low-altitude orbiter of the BepiColombo mission. The UV instrument, consisting of the two spectrometers with common electronics, aims at measuring (1) emission lines from molecules, atoms and ions present in the Mercury’s tenuous atmosphere and (2) the reflectance spectrum of Mercury’s surface. The instrument pursues a complete coverage in UV spectroscopy. The extreme UV spectrometer covers the spectral range of 30–150 nm with the field of view of 5.0°, and the spectrum from 130 to 430 nm is obtained by the far UV spectrometer. The extreme UV spectrometer employs multi-layer coating technology to enhance its sensitivity at particular emission lines. This technology enables us to identify small ionospheric signatures such as He II (30.4 nm) and Na II (37.2 nm), which could not be detected with conventional optics.     

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.     

氧气A(0,0)波段气辉体发射率和临边辐射强度模拟与分析

临近空间大气参数如温度、密度、风场等对预报模型精度及航天器运行安全等有较大的影响,而气辉的辐射模拟是大气参数反演的重要过程.本文基于光化学模型计算了氧气A（0,0）波段气辉的体发射率和临边辐射强度.基于氧气A（0,0）波段气辉的光化学反应机制、大气动力学和光化学反应理论,建立产生O₂（b1Σ_g+）的光化学模型.计算气辉体发射率,基于临边探测几何路径进行气辉辐射强度模拟.体发射率计算结果与AURIC模型结果的辐射值及辐射高度均一致.基于计算和模拟结果,对氧气A波段气辉体发射率和辐射强度的影响因素进行了分析.      

Observations of the ozone and nitrogen dioxide profiles in the TROICA-4 experiment

To investigate the vast area of Russia, a mobile scientific facility based in a railway carriage was developed. It is capable to perform continues measurements being coupled in a passenger train traveling along railroads. It was first equipped with a spectrometer for remote sensing of ozone and nitrogen dioxide in the atmosphere for the transcontinental observations into the chemistry of the atmosphere-4 expedition performed from February 18 to March 5, 1998. A twilight DOAS method, which was applied for retrieval of the nitrogen dioxide profiles basing on spectral measurements at the visible wavelengths (434–451 nm), is described in the paper. Main features of a new algorithm for retrieval of the ozone profile and total content using the differential structure of the UV spectrum (310–335 nm) are presented. The ozone and nitrogen dioxide contents are obtained and shortly validated against available alternative data.     

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.     

Laboratory simulation of the photoprocessing and warm-up of cometary and pre-cometary ices: production and analysis of complex organic molecules.

The possibility that the organic molecules that have been found near comets could have formed by UV photolysis of interstellar ices was investigated by simulating this process in the laboratory. It is found that oxygen rich organics containing C-OH, C-H and C=O groups are readily produced in this way. These results indicate that part of the organic material in comets may have formed by UV irradiation of ices, either in the pre-solar nebula or in the interstellar phase.