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.     

New planetary atmosphere simulations: application to the organic aerosols of Titan.

The atmosphere of Titan partly consists of hazes and aerosol particles. Experimental simulation is one of the powerful approaches to study the processes which yield these particles, and their chemical composition. It provides laboratory analogues, sometimes called tholins. Development and optimization of experimental tools were undertaken in order to perform chemical and physical analyses of analogues under conditions free from contamination. A "Titan aerosol generator" was developed in the frame of the Cassini-Huygens mission, in order to produce Titan's aerosol analogues within conditions closer to those of the titanian atmosphere: cold plasma simulation system, low pressure and low temperature. The direct current (DC) glow discharge is produced by applying a DC voltage between two conductive electrodes inserted into the gas mixture-model of the studied atmosphere- at low pressure. A high-impedance power supply is used to provide the electrical field. All the system is installed in a glove box, which protect samples from any contamination. Finally the research program expected with this new material is presented.     

The low temperature organic chemistry of Titan's geofluid.

Organic chemistry on Titan and prebiotic chemistry on Earth involve the same N-containing organics: nitriles and their oligomers. Couplings of their chemistry in the three parts of Titan's geofluid (atmosphere, aerosols and surface) seem to play a key role in the organic chemical evolution of the planet. If liquid water was present on Titan, then a prebiotic chemistry, involving eutectics, similar to that of the early Earth, may have occurred. However, liquid water is currently absent and a prebiotic chemistry based only on N-organics may be evolving now on Titan. The other consequence of the low temperatures of Titan is the possible formation of organics unstable at room temperature and very reactive. So far, these compounds have not been systematically searched for in experimental studies of Titan's organic chemistry. C4N2 has already been detected on Titan. Powerful reactants in organic chemistry, CH2N2, and CH3N3, may be also present. They exhibit spectral signatures in the mid-IR strong enough to allow their detection at the 10-100 ppb level. They may be detectable on future IR spectra (ISO and Cassini) of Titan.     

Titan's atmosphere composition: certainties and speculations.

Firm results concerning the thermal structure, the composition, the seasonal effects of the atmosphere of Titan, as well as the superotation of its stratosphere are reviewed. The nature of the surface of the satellite, the possible presence of argon in the atmosphere and the structure and composition of clouds and aerosols are, among other topics, still speculative. The implications of the observed deuterium enrichment on the origin of ices in the outer part of the nebula are controversial.     

Corona discharge of Titan's troposphere.

The atmosphere of Titan is constantly bombarded by galactic cosmic rays and Saturnian magnetospheric electrons causing the formation of free electrons and primary ions, which are then stabilized by ion cluster formation and charging of aerosols. These charged particles accumulate in drops in cloud regions of the troposphere. Their abundance can substantially increase by friction, fragmentation or collisions during convective activity. Charge separation occurs with help of convection and gravitational settling leading to development of electric fields within the cloud and between the cloud and the ground. Neutralization of these charge particles leads to corona discharges which are characterized by low current densities. These electric discharges could induce a number of chemical reactions in the troposphere and hence it is of interest to explore such effects. We have therefore, experimentally studied the corona discharge of a simulated Titan's atmosphere (10% methane and 2% argon in nitrogen) at 500 Torr and 298 K by GC-FTIR-MS techniques. The main products have been identified as hydrocarbons (ethane, ethyne, ethene, propane, propene + propyne, cyclopropane, butane, 2-methylpropane, 2-methylpropene, n-butene, 2-butene, 2,2-dimethylpropane, 2-methylbutane, 2-methylbutene, n-pentane, 2,2-dimethylbutane, 2-methylpentane, 3-methylpentane, n-hexane, 2,2-dimethylhexane, 2,2-dimethylpentane, 2,2,3-trimethylbutane, 2,3-dimethylpentane and n-heptane), nitriles (hydrogen cyanide, cyanogen, ethanenitrile, propanenitrile, 2-methylpropanenitrile and butanenitrile) and an uncharacterized film deposit. We present their trends of formation as a function of discharge time in an ample interval and have derived their initial yields of formation. These results clearly demonstrate that a complex organic chemistry can be initiated by corona processes in the lower atmosphere. Although photochemistry and charged particle chemistry occurring in the stratosphere can account for many of the observed hydrocarbon species in Titan, the predicted abundance of ethene is to low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, its production by corona processes and subsequent diffusion into the stratosphere appears to be an adequate source. Because little UV penetrates to the lower atmosphere to destroy the molecules formed there, the corona-produced species may be long-lived and contribute significantly to the composition of the lower atmosphere and surface.     

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.     

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.     

An adequate kinetic model of photochemical aerosol formation in Titan's atmosphere.

The photochemistry of hydrocarbons in Titan's atmosphere is modeled by a comprehensive kinetic scheme, containing 732 elementary reactions and 147 species up to C60. Four groups of the hydrocarbons are considered: Polyacetylenes (PA), Polyvinyles (PV), Vinylacetylenes (VA) and Allenes (Polyenes).     

Production of hydrocarbons and nitriles by electrical processes in Titan's atmosphere.

Although lightning has not been observed in Titan's atmosphere, the presence of methane rain in the troposphere suggests the possibility of electrical activity in the form of corona and/or lightning discharges. Here we examine the chemical effects of these electrical processes on a Titan simulated atmosphere composed of CH4 in N2 at various mixing ratios. Corona discharges were simulated in two different experimental arrays. For the detection of reactive intermediates we used a mass spectrometer to study the main positive ions arising by bombarding low-energy electrons from a hot filament into low-pressure methane. The final stable products, generated by applying a high voltage in a coaxial reactor with either positive or negative polarity, were separated and detected by gas chromatography-Fourier transform infrared spectroscopy and electron impact mass spectrometry (GC-FTIR-MS). Lightning discharges were simulated by a hot and dense plasma generated by a Nd-YAG laser and the final products were separated and detected by GC-FTIR-MS. Corona discharges produce linear and branched hydrocarbons as well as nitriles whereas lightning discharges generate mainly unsaturated hydrocarbons and nitriles. Lightning discharges are about 2 orders of magnitude more efficient in product formation than corona discharges.     

Possible contribution of different energy sources to the production of organics in Titan's atmosphere.

A quantitative comparison of the products arising from the irradiation of a Titan's simulated atmosphere is presented. The energy sources used represent some of the main events that occur in the satellite's atmosphere. All of the compounds identified are classified in the hydrocarbon and nitrile chemical families. Almost all of the detected compounds in Titan's atmosphere are produced by one or more energy sources. The compounds with the highest energy yields include the C2 hydrocarbons, methanonitrile and ethanonitrile. The possibility of using some of the produced organics as tracer compounds during the Huygens descend to identify the leading energy form in the different atmospheric levels remains open.     

IR and UV spectroscopic data for polyynes: predictions for long carbon chain compounds in Titan's atmosphere.

A better understanding of the complex organic chemistry occurring in the methane rich atmosphere of Titan can be achieved via the comparison of observations with results obtained by theoretical models. Available observations are still few but their analysis requires the knowledge of a large set of data, namely frequencies and absolute band intensities. Cross sections are also needed to develop the chemical schemes of photochemical models, in particular the schemes leading to the formation of haze particles visible on Titan. Unfortunately, some of these parameters are not well known, especially if one takes into account the extreme physical conditions of the studied object. This lack of data is particularly enhanced for polyynes because these compounds are highly unstable at the usual pressure and temperature conditions of a laboratory and therefore are very difficult to study. We have developed UV and IR studies, coupling experimental and theoretical approaches, in order to extrapolate the parameters available for short polyynes to longer carbon chains. In the mid-UV range, when the length of the chain increases, the absorption system of polyynes is shifted to longer wavelength and its oscillator strength increases linearly. In the IR range, with the increase of the number of carbon bonds, the positions of the CCC and CCH bending modes shift to lower energy, the latest converging rapidly to a fixed value of 620.5 cm-1 for an infinite length polyyne. Implications for detection and evolution of polyynes in Titan's atmosphere are emphasised.     

The role of aerosols in the climate system: Results of numerical experiments in climate models

Three principal questions are recurrent with the consideration of an aerosol related climatic effect: (1) do aerosols heat or cool the atmosphere, (2) are aerosol climatic effects significant and (3) can numerical models be validated by predicting a climatic change associated with a measured aerosol-event. Each of these questions will be addressed from a historical perspective. In addition, the most recent aerosol-related modeling will be discussed as well as recommendations for future research.     

The role of volcanic aerosols and relativistic electrons in modulating winter storm vorticity

Small changes in the vorticity of winter storms, responding to solar wind variations, are found in winters from 1957 to 2011, and are greater for winters with higher levels of stratospheric volcanic aerosols. Using 1993–2011 data, the response of the vorticity area index (VAI) is shown to be of larger amplitude when the days of minima in the relativistic electron flux (REF) precipitating from the radiation belts are used, instead of heliospheric current sheet (HCS) crossings, as key days in superposed epoch analyses. The HCS crossings mostly occur within a few days of the REF minima. The VAI is an objective measure of the area of high cyclonic vorticity, and for the present work is derived from ERA-40 and ERA-Interim reanalyses of global meteorological data. The VAI dependencies on the stratospheric aerosol content (SAC) and the REF are consistent with a model in which the ionosphere-earth current density (J_z) affects cloud microphysics. One of the ways in which J_z is modulated is by changes in stratospheric column resistance (S), which is increased by stratospheric aerosols. Because S is in series with the tropospheric column resistance (T), J_z modulation by REF requires that S be not negligible with respect to T. So the J_z modulation and the VAI response appear when the SAC is very high, or the REF reductions (which also increase S) are very deep, and when the product of the SAC and the reciprocal of the REF exceeds a threshold value dependent on T.     

Ground-based simulations of galactic cosmic ray fragmentation and transport.

Since mean free paths for nuclear fragmentation are of the order of the ranges of primary Galactic Cosmic Ray (GCR) nuclei, determination of the radiation field produced by successive fragmentations of nuclei in material and tissue is essential to accurate assessment of GCR radiation risk to humans on long-duration missions outside the geomagnetosphere. We describe some recent measurements made at the Bevalac of heavy ion transport through materials, with representative results and examples of how they may be applied to aspects of the space radiation problem, including efforts to devise analytical tools for predicting biological effects and for designing spacecraft shielding.     

Propagation and interaction of interplanetary transient disturbances. Numerical simulations

We study the heliocentric evolution of ICME-like disturbances and their associated transient forward shocks (TFSs) propagating in the interplanetary (IP) medium comparing the solutions of a hydrodynamic (HD) and magnetohydrodynamic (MHD) models using the ZEUS-3D code [Stone, J.M., Norman, M.L., 1992. Zeus-2d: a radiation magnetohydrodynamics code for astrophysical flows in two space dimensions. i – the hydrodynamic algorithms and tests. Astrophysical Journal Supplement Series 80, 753–790]. The simulations show that when a fast ICME and its associated IP shock propagate in the inner heliosphere they have an initial phase of about quasi-constant propagation speed (small deceleration) followed, after a critical distance (deflection point), by an exponential deceleration. By combining white light coronograph and interplanetary scintillation (IPS) measurements of ICMEs propagating within 1 AU [Manoharan, P.K., 2005. Evolution of coronal mass ejections in the inner heliosphere: a study using white-light and scintillation images. Solar Physics 235 (1–2), 345–368], such a critical distance and deceleration has already been inferred observationally. In addition, we also address the interaction between two ICME-like disturbances: a fast ICME 2 overtaking a previously launched slower ICME 1. After interaction, the leading ICME 1 accelerates and the tracking ICME 2 decelerates and both ICMEs tend to arrive at 1 AU having similar speeds. The 2-D HD and MHD models show similar qualitative results for the evolution and interaction of these disturbances in the IP medium.     

The nature of nonthermal X-ray filaments near the galactic center

Recent Chandra and XMM-Newton observations reported evidence of two X-ray filaments G359.88−0.08 (SgrA-E) and G359.54+0.18 (the ripple filament) near the Galactic center. The X-ray emission from these filaments has a nonthermal spectrum and coincides with synchrotron emitting radio sources. Here, we report the detection of a new X-ray feature coincident with a radio filament G359.90−0.06 (SgrA-F) and show more detailed VLA, Chandra and BIMA observations of the radio and X-ray filaments. In particular, we show that radio emission from the nonthermal filaments G359.90−0.06 (SgrA-F) and G359.54+0.18 (the ripple) has a steep spectrum whereas G359.88−0.08 (SgrA-E) has a flat spectrum. The X-ray emission from both these sources could be due to synchrotron radiation. However, given that the 20 km s⁻¹ molecular cloud, with its intense 1.2 mm dust emission, lies in the vicinity of SgrA-F, it is possible that the X-rays could be produced by inverse Compton scattering of far-infrared photons from dust by the relativistic electrons responsible for the radio synchrotron emission. The production of X-ray emission from ICS allows an estimate of the magnetic field strength of 0.08 mG within the nonthermal filament. This should be an important parameter for any models of the Galactic center nonthermal filaments.     

Numerical simulation of organic compounds formation in planetary atmospheres: comparison with laboratory experiments.

A numerical model of CH4 and CH4-NH3 photochemistry at 147 nm has been developed and results are directly compared with experimental simulations carried out for the same mixtures. Simulations with varying quantities of ammonia and hydrogen show how amines and nitriles can be produce in planetary atmospheres. These comparisons allow one to test schemes of reactions used in photochemical models. In particular, it is shown that the scheme of reactions of CH4 is fairly well consistent with experimental data. On the other hand, the photochemistry of NH3 should be improved.     

The CEEF, closed ecosystem as a laboratory for determining the dynamics of radioactive isotopes.

Nuclear power generation is now confronted with a very difficult situation all over the world because of the problems of radioactive waste disposal and of the accidents, which have occurred. Nuclear power generation now supplies nearly 30% of total electric power demand in Japan. Therefore it is very difficult to change quickly the construction plans of nuclear facilities already designed. A nuclear fuel reprocessing center is now under construction in Rokkasho-Mura in Aomori Prefecture. If this center starts its operation, small amounts of 14CO2 are expected to be released into the atmosphere and will enter the global cycle. The simulation experiment of 14C trace amounts which enter into ecosystems is now being planned using stable isotope 13C within CEEF (Closed Ecology Experiment Facilities).     

The effect of aerosols on climate and aerosol climatology on the basis of observations from space

Principal aspects of the effect of aerosols on climate are discussed and the possibilities of obtaining a climatic data set of global aerosols are analyzed. Based on the analysis of space images, new data have been obtained on gigantic dust outbreaks in various regions of the Earth. It has been shown that dust outbreaks can propagate over hundreds and sometimes thousands of kilometers. The western Sahara - Atlantic Ocean is the major region of propagation of these outbreaks. The continent-to-continent trajectories of dust clouds have been discovered (from Africa to the coast of America, from Central Asia to the Pacific Ocean). Maps of the sources of strong dust transformations have been studied and drawn. In particular, an anthropogenic dust source has been found out on the northeastern coast of the Aral Sea. A striped mesostructure of dust formations has been analyzed, determined by both the inhomogeneous surface and peculiarities of the eddy dust transport. The techniques have been discussed in detail for retrieving the parameters of aerosol size distribution and the vertical profiles of the coefficients of aerosol extinction in the stratosphere and lower mesosphere from the data on the brightness of the twilight and daytime horizon as well as occultation measurements of solar radiation attenuation by the atmosphere.The difficulty of reliably predicting possible environmental changes arises both from the problems of estimating complex interactions of numerous processes and from a lack of information concerning various environmental parameters. For example, an important factor in present day climatic changes is the increased dust content of the atmosphere due to man's activities. However, a reliable estimate of this influence is found to be impossible due to the absence of definitive data on the global distribution of atmospheric dust and the properties of dust in various parts of the world [4,5,13–15]. The impact of aerosols on climate has been discussed in detail in a number of monographs [12–15].Observations from space have opened up new possibilities for studying atmospheric dust. For this purpose, both the imagery and spectrometry of the Earth's atmosphere from space are used. Rather attractive are the prospects for laser sounding [1].