Laboratory experiments in the study of the chemistry of the outer planets.

The investigation of chemical evolution of bodies in our solar system has, in the past, included observations, theoretical modeling, and laboratory simulations. Of these programs, the last one has been the most criticized due to the inherent difficulties in accurately recreating alien environments in the laboratory. Processes such as wall reactions and changes in chemistry due to difficulties in achieving realistic conditions of temperature, pressure, composition, and energy flux may yield results which are not truly representative of the systems being modeled. However, many laboratory studies have been done which have yielded data useful in planetary science. Gross simulations of atmospheric chemistry have placed constraints on the nature of complex molecules expected in planetary atmospheres. More precise studies of specific chemical processes have provided information about the sources and properties of product gases and aerosols. Determinations of basic properties such as spectral features and reaction rate constants yield data useful in the interpretation of observations and in computational modeling. Alone, and in conjunction with modeling, laboratory experiments will continue to be used to further our understanding of the outer solar system, and some experiments that need to be done are listed.     

Radiation chemistry of ices of planetological interest at low temperature.

We present the results of recent experiments on some physico-chemical effects induced by fast ion colliding with solids of relevance for the physics of planetary objects. The production of molecular solids, polymer-like materials and amorphous carbon by irradiation of frozen hydrocarbons and pentacene is discussed. We also report on a set of experimental results obtained irradiating methanol and water-methanol mixtures. Because of bombardment different species form. The techniques used for the analysis are "in situ" infrared (IR) and Raman spectroscopy. The experimental results are finally discussed in the light of their relevance for planetary physics.     

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.     

Carbonaceous materials in cometary environments: the case of the 3-4 micrometers bands.

We present in this paper a simulation of cometary spectra between 3 and 4 micrometers performed by using the optical properties of various carbon-based materials measured at different temperatures in the range 300-520 K. In our computations we have used new laboratory data obtained for hydrogenated amorphous carbon (HAC) grains and three kinds of polycyclic aromatic hydrocarbons (PAHs). All these materials show significant features in the near IR region; however, only the synthetic spectra obtained from HAC grains show a satisfactory agreement with the profile of the cometary bands.     

Origin of organic matter in the protosolar nebula and in comets.

Comet organics are traced to their origin in interstellar space. Possible sources of comet organics from solar nebula chemistry are briefly discussed. The infrared spectra of interstellar dust are compared with spectra of solar (space) irradiated laboratory organic residues and with meteorites. The spectra compare very favorably. The atomic composition of first generation laboratory organic residues compares favorably with that of comet Halley organics if divided into appropriate "volatile" (less refractory) and "refractory" (more refractory) complex organics.     

XANES analysis of organic residues produced from the UV irradiation of astrophysical ice analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogen- and oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.     

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.     

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.     

Quantum chemical calculations of infrared spectra for the identification of unknown compounds by GC/FTIR/MS in exobiological simulation experiments.

Gas chromatography/Fourier transform IR spectroscopy/mass spectrometry (GC/FTIR/MS) is a powerful tool for the separation and unambiguous identification of complex mixtures of organic compounds, where the use of two kinds of spectra allows to significantly increase identification reliability. The simplest situation is when acquired spectra can be found in IR and MS databases, or appropriate standards are available; but this is not always the case. Some simulation experiments related to the origins of life and exobiology (e.g., simulation of amino acid pyrolysis during atmospheric entry of space bodies) can be a typical example when one encounters with numerous unknown compounds. To assist their identification by GC/FTIR/MS, recently we suggested quantum chemical calculations of infrared spectra in order to compare them to IR spectra acquired experimentally. The present work summarizes the results obtained by semi-empirical and ab initio methods, discusses their advantages and limitations, considering as test compounds some cyclic amides and amidines derived from amino acids, saturated and unsaturated nitriles (including those of interest for the Titan atmospheric chemistry), acetylenes and some other nitrogen compounds.     

Assimilation of Mars Global Surveyor meteorological data

The Mars Global Surveyor (MGS) Mission is more than just a return to Mars. It represents a qualitatively new type of planetary mission. This is true not only because of the capable instrumentation aboard the spacecraft and the choice of orbit and data rate, but also because of a major beneficial change in our understanding of the interplay between observation and modeling. The Thermal Emission Spectrometer (TES), for example, is capable of taking thousands of infrared spectra per day. The 15 micrometer carbon dioxide band in these spectra can be inverted to obtain atmospheric temperature profiles, amounting to some 15,000–25,000 separate measurements each day. In addition, radio occultations produce fewer, but much higher resolution, temperature and pressure profiles. How is such a quantity of data to be handled? Clearly not in the old-fashioned manner in which a single profile is studied at great length and detail. The quantity of data does not allow this; and the quality of the data does not support it. (A single atmospheric profile is bound to contain small-scale spatial and temporal variation—e.g., gravity waves—that cannot be removed unambiguously, as well as possible errors due to noise in the observations or non-uniqueness of the inversions). Furthermore, much of the atmospheric science of interest (winds, for example) depends on quantities like horizontal temperature gradients that are not directly observed. Instead, the data should be examined collectively with the aid of a model that incorporates our knowledge of the governing physics. Described here are the first results of such a data assimilation exercise with TES observations during the aerobraking hiatus period at L_s ≈ 200.     

Miniaturized laser-induced plasma spectrometry for planetary in situ analysis – The case for Jupiter’s moon Europa

Jupiter’s icy moon Europa is one of most promising places in our Solar System where possible extraterrestrial life forms could exist either in the past or even presently. The Europa Lander mission, an exciting part of the international Europa Jupiter System Mission (EJSM/Laplace), considers in situ planetary exploration of the moon. The distance of Europa from the Earth and the Sun asks for autonomous analytical tools that maximize the scientific return at minimal resources, demanding new experimental concepts. We propose a novel instrument, based on the atomic spectroscopy of laser generated plasmas for the elemental analysis of Europa’s surface materials as far as it is in reach of the lander for example by a robotic arm or a mole, or just onboard the lander. The technique of laser-induced plasma spectrometry provides quantitative elemental analysis of all major and many trace elements. It is a fast technique, i.e. an analysis can be performed in a few seconds, which can be applied to many different types of material such as ice, dust or rocks and it does not require any sample preparation. The sensitivity is in the range of tens of ppm and high lateral resolution, down to 50 μm, is feasible. In addition, it provides the potential of depth profiling, up to 2 mm in rock material and up to a few cm in more transparent icy matrices. Key components of the instrument are presently developed in Germany for planetary in situ missions. This development program is accompanied by an in-depth methodical investigation of this technique under planetary environmental conditions.     

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.     

From the interstellar clouds, through the inner to the outer solar system: a universally distributed complex organic chemistry. Preface.

High molecular weight organic compounds are involved in the chemistry and physics of many astrophysical and planetary objects. They are or should be present in interstellar dust, in comets and meteorites, in the Giant planets and Titan, in asteroids Triton and icy satellites. They represent a class of very complex organic material, part of which may have played a role in the origin of life on Earth. Thus they directly concern prebiotic chemistry and exobiology.     

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.     

Low-altitude,near-polar and near-circular orbits around Europa

The dynamics of orbits around planetary satellites, taking into account the gravitational attraction of a third-body and the non-uniform distribution of mass of the planetary satellite, is studied. The Hamiltonian considered is explicitly time-dependent. Conditions for frozen orbits are presented. Low-altitude, near-polar orbits, very desirable for scientific missions to study planetary satellites such as the Jupiter’s moon Europa, are analyzed. Lifetimes for these orbits are computed through the single and double averaged method. Comparison between the results obtained by the single and double averaged method is presented. The single-averaged model is more realistic, since it does not eliminate the term due to the equatorial ellipticity of the planetary satellite as done by the double-averaged problem. Considering the single-averaged method, we found unstable frozen orbits where the satellite does not impact with the surface of Europa for at least 200 days. We present an approach using the unaveraged disturbing potential to analyze the effects of these terms in the amplitude of the eccentricity.     

Synergies of Earth science and space exploration

A more flexible policy basis from which to manage our planet in the 21st century is desirable. As one contribution, we note that synergies between space exploration and the preservation of our habitat exist, and that protecting life on Earth requires similar concepts and information as investigations of life beyond the Earth, including the expansion of human presence in space. Instrumentation and data handling to observe both planetary objects and planet Earth are based on similar techniques. Moreover, while planetary surface operations are conducted under different conditions, the technology to probe the surface and subsurface of both the Earth and other planets requires similar tools, such as radar, seismometers, and drilling devices. The Earth observation community has developed some exemplary tools and has featured successful international cooperation in data handling and sharing that could be equally well applied to robotic planetary exploration. Here we propose a network involving both communities that will enable the interchange of scientific insights and the development of new policies and management strategies. Those tools can provide a vital forum through which the management of this planet can be assisted, and in which a new bridge between the Earth-centric and space-centric communities can be built.     

Dark matter in the outer solar system.

There are now a large number of small bodies in the outer solar system that are known to be covered with dark material. Attempts to identify that material have been thwarted by the absence of discrete absorption features in the reflection spectra of these planetesimals. An absorption at 2.2 micrometers that appeared to be present in several objects has not been confirmed by new observations. Three absorptions in the spectrum of the unusually red planetesimal 5145 Pholus are well-established, but their identity remains a mystery.     

Present situation in the identification of polycyclic aromatic hydrocarbons

Recently, the interpretation given to the so-called “unidentified” infrared emission bands has drastically improved. These bands are attributed to the fundamental vibrations of large molecules known in organic chemistry as Polycyclic Aromatic Hydrocarbons (PAH's). In this paper, we review the main arguments which led to this conclusion and focus our attention to some recent IR and UV spectroscopic studies which allow us to interpret further the main characteristics of astronomical spectra.     

我国中低纬地区上空低电离层中的行星波

本文通过5年的电离层吸收观测资料与平流层增温事件对比及吸收资料的谱分析,得出以下几点初步结论:1)极区平流层增温事件的影响可能通过子午环流和行星波传播,经过5—9天后到达中低纬地区,从而引起那里的电离层吸收变化;2)冬季行星波沿子午方向的平均速度大约在10m/s到15m/s之间变化;3)全年均有周期为32天、18天、10天、8天和2天的行星波出现,它对大气湍流系数有明显影响。计算得出行星波扰动引起中层的NO浓度偏离未扰值可高达40%。      

Late stages of stellar evolution – Herschel’s contributions

Cool objects glow in the infrared. The gas and solid-state species that escape the stellar gravitational attraction of evolved late-type stars in the form of a stellar wind are cool, with temperatures typically ?1500 K, and can be ideally studied in the infrared. These stellar winds create huge extended circumstellar envelopes with extents approaching 10¹⁹${10}^{19}$ cm. In these envelopes, a complex kinematical, thermodynamical and chemical interplay determines the global and local structural parameters. Unraveling the wind acceleration mechanisms and deriving the complicated structure of the envelopes is important to understand the late stages of evolution of ∼97% of stars in galaxies as our own Milky Way. That way, we can also assess the significant chemical enrichment of the interstellar medium by the mass loss of these evolved stars. The Herschel Space Observatory is uniquely placed to study evolved stars thanks to the excellent capabilities of the three infrared and sub-millimeter instruments on board: PACS, SPIRE and HIFI. In this review, I give an overview of a few important results obtained during the first two years of Herschel observations in the field of evolved low and intermediate mass stars, and I will show how the Herschel observations can solve some historical questions on these late stages of stellar evolution, but also add some new ones.