Hydrogen cyanide polymers from the impact of comet P/Shoemaker-Levy 9 on Jupiter.

Hydrogen cyanide polymers--heterogeneous solids ranging in color from yellow to orange to brown to black--may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orange-brown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to alpha-amino acids. Other polymers and multimers with ladder structures derived from HCN would also be present and might well be the source of the many nitrogen heterocycles, adenine included, detected by thermochemolytic analysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter could therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized from freshly formed HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.     

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.     

Hydrogen cyanide polymers on comets.

The original presence on cometary nuclei of frozen volatiles such as methane, ammonia and water makes them ideal sites for the formation and condensed-phase polymerization of hydrogen cyanide. We propose that the non-volatile black crust of comet Halley consists largely of such polymers. Dust emanating from Halley's nucleus, contributing to the coma and tail, would also arise partly from these solids. Indeed, secondary species such as CN have been widely detected, as well as HCN itself and particles consisting only of H, C and N. Our continuing investigations suggest that the yellow-orange-brown-black polymers are of two types: ladder structures with conjugated -C=N- bonds, and polyamidines readily converted by water to polypeptides. These easily formed macromolecules could be major components of the dark matter observed on the giant planets Jupiter and Saturn, as well as on outer solar system bodies such as asteroids, moons and other comets. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers either through cometary bombardment or by terrestrial happenings of the kind that brought about the black crust of Halley. The resulting proteinaceous matrix could have promoted the molecular interactions leading to the emergence of life.     

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.     

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.     

Infrared spectroscopy of organics of planetological interest at low temperatures.

In the context of prebiotic chemistry in space, some of the outer planetary objects display H, C, N and O rich chemistry similar to the one in the biosphere of Earth. Of particular interest are Saturn's moon, Titan; Neptune's moon, Triton; and Pluto where extreme cold conditions prevail. Identifications of chemical species on these objects (surfaces and atmospheres) is essential to a better understanding of the radiation induced chemical reactions occurring thereon. There have been several ground based observations of these planetary objects in the infrared windows from 1 to 2.5 micrometers. Voyager also provided spectra in the thermal infrared (6 to 50 micrometers) region. Interpretation of these data require laboratory infrared spectra of relevant species under the temperature conditions appropriate to these objects. The results of some of these studies carried out in our laboratory and elsewhere and their impact on the analyses of the observed data will be summarized.     

The origin of sulfur-bearing species on the surfaces of icy satellites

We present experimental results in order to understand the physico-chemical effects induced by fast ions irradiating sulfur bearing molecules. The experiments are relevant both to Solar System objects (icy satellites, comets, TNOs) and icy mantles on grains in the interstellar medium. Here we concentrate on the application to the Galilean moons that are exposed to high energetic particle fluxes in the jovian magnetosphere.     

Organics produced by ion irradiation of ices: some recent results.

Some results, recently obtained from laboratory experiments of ion irradiation of ice mixtures containing H, C, N, and O, are here summarized. They are relevant to the formation and evolution of complex organics on interstellar dust, comets and other small bodies in the external Solar System. In particular the formation of CN-bearing species is discussed. Interstellar dust incorporated into primitive Solar System bodies and subsequently delivered to the early Earth, may have contributed to the origin of life. The delivery of CN-bearing species seems to have been necessary because molecules containing the cyanogen bond are difficult to be produced in an environment that is not strongly reducing as that of the early Earth probably was. Moreover we report on an ongoing research program concerning the interaction between refractory materials produced by ion irradiation of simple ices and biological materials (amino acids, proteins, cells).     

Search for organic molecules in the outer solar system

Recent developments of millimeter astronomy have led to the discovery of more and more complex molecules in the interstellar medium. In a similar way, attempts have been made to detect complex molecules in the atmospheres of the most primitive bodies of the Solar System, i.e. outer planets and comets, as well as in Titan's atmosphere. An important progress has been achieved thanks to the continuous development of infrared astronomy, from the ground and from space vehicles. In particular, an important contribution has come from the IRIS-Voyager infrared spectrometer with the detection of prebiotic molecules on Titan, and some complex organic molecules on Jupiter and Saturn. Another important result has been the observation of carbonaceous material in the immediate surroundings of Comet Halley's nucleus. In the near future, the search for organic molecules in the outer Solar System should benefit from the developments of large millimeter antennae, and in the next decade, from the operation of infrared Earth-orbiting spacecrafts (ISO, SIRTF).     

Hopper concepts for small body landers

The investigation of small bodies, comets and asteroids, can contribute substantially to our understanding of the formation and history of the Solar System. In situ observations by landers play an important role in this field.     

Prebiotic syntheses of purines and pyrimidines

The work done in many laboratories during the last two decades has confirmed that hydrogen cyanide and cyanoacetylene are the two major precursors for the prebiotic synthesis of purines and pyrimidines, respectively. Although several different pathways for the synthesis of purines have been described, they are all variations of the initial mechanism proposed by Oró and Kimball, where hydrogen cyanide leads first to the formation of a 4,5-disubstituted imidazole derivative, and then to the closing of the purine ring with a C₁ compound. A number of experiments have shown that purines and pyrimidines can also be obtained from methane, ammonia (nitrogen), and water mixtures, provided an activating source of energy (radiation, electric discharges, etc.) is available. However, in this case the yields are lower by about two orders of magnitude because of the intermediate formation of hydrogen cyanide and cyanoacetylene. The latter two compounds have been found in interstellar space, Titan and other bodies of the solar system. They were probably present in the primordial parent bodies from the solar nebula in concentrations of 10⁻² to 10⁻³ M as inferred from recent calculations by Miller and coworkers obtained for the Murchison meteorite. These concentrations should have been sufficient to generate relatively large amounts of purine and pyrimidine bases on the primitive Earth.     

Surface elements and landing strategies for small bodies missions – Philae and beyond

The investigation of small bodies, comets and asteroids, can contribute substantially to our understanding of the formation and history of the Solar System. In-situ observations by Landers play a prominent role in this field.The Rosetta Lander – Philae – is currently on its way to comet 67P/Churyumov–Gerasimenko. It will land in November 2014 and perform numerous experiments with a suite of 10 scientific instruments.Philae has been designed to cope with a wide range of possible comet properties. The considerations taken during its development are relevant for future Lander missions to small bodies in the Solar System.In addition the paper provides a review of alternative concepts, studied or developed for various missions like Phobos, Hayabusa/Minerva or Géocroiseur/Leonard.Various missions to small bodies in the Solar System, including Landers, are currently studied (e.g., Marco Polo). The paper will address the mission options and compare applicable technologies with the solutions chosen for Philae.     

Organic solids produced from simple C/H/O/N ices by charged particles: applications to the outer solar system.

CH4, CO, and CO2 are all potential one-carbon molecular repositories in primitive icy objects. These molecules are all found in the Comet Halley coma, and are probable but, (except for CH4 detected on Triton and Pluto) undetected subsurface constituents in icy outer solar system objects. We have investigated the effects of charged particle irradiation by cold plasma discharge upon surfaces of H2O:CH4 clathrate having a 200:1 ratio, as well as upon ices composed of H2O plus C2H6 or C2H2 (sometimes plus NH3) which are also plausible constituents. These materials color and darken noticeably after a dose 10(9) - 10(10) erg cm-2, which is deposited rapidly (< or = 10(4) yr.) in solar system environments. The chromophore is a yellowish to tan organic material (a tholin) which we have studied by UV-VIS reflection and transmission, and IR transmission spectroscopy. Its yield, -1 C keV-1, implies substantial production of organic solids by the action of cosmic rays and radionuclides in cometary crusts and interiors, as well as rapid production in satellite surfaces. This material shows alkane bands which Chyba and Sagan have shown to well match the Halley infrared emission spectrum near 3.4 microns, and also bands due to aldehyde, alcohol and perhaps alkene/aromatic functional groups. We compare the IR spectral properties of these tholins with the spectra of others produced by irradiation of gases and ices containing simple hydrocarbons.     

Thermal protection system development,testing, and qualification for atmospheric probes and sample return missions: Examples for Saturn,Titan and Stardust-type sample return

The science community has continued to be interested in planetary entry probes, aerocapture, and sample return missions to improve our understanding of the Solar System. As in the case of the Galileo entry probe, such missions are critical to the understanding not only of the individual planets, but also to further knowledge regarding the formation of the Solar System. It is believed that Saturn probes to depths corresponding to 10 bars will be sufficient to provide the desired data on its atmospheric composition. An aerocapture mission would enable delivery of a satellite to provide insight into how gravitational forces cause dynamic changes in Saturn’s ring structure that are akin to the evolution of protoplanetary accretion disks. Heating rates for the “shallow” Saturn probes, Saturn aerocapture, and sample Earth return missions with higher re-entry speeds (13–15 km/s) from Mars, Venus, comets, and asteroids are in the range of 1–6 KW/cm². New, mid-density thermal protection system (TPS) materials for such probes can be mission enabling for mass efficiency and also for use on smaller vehicles enabled by advancements in scientific instrumentation. Past consideration of new Jovian multiprobe missions has been considered problematic without the Giant Planet arcjet facility that was used to qualify carbon phenolic for the Galileo probe. This paper describes emerging TPS technologies and the proposed use of an affordable, small 5 MW arcjet that can be used for TPS development, in test gases appropriate for future planetary probe and aerocapture applications. Emerging TPS technologies of interest include new versions of the Apollo Avcoat material and a densified variant of Phenolic Impregnated Carbon Ablator (PICA). Application of these and other TPS materials and the use of other facilities for development and qualification of TPS for Saturn, Titan, and Sample Return missions of the Stardust class with entry speeds from 6.0 to 28.6 km/s are discussed.     

METHIS: Mercury thermal infrared spectrometer

The BepiColombo mission to Mercury is devoted to the thorough exploration of Mercury and its environment, with the aim to understand the processes of planetary formation and evolution in the hottest part of the protoplanetary nebula. This mission represents an unique opportunity for the European community to extend the understanding of the Solar Nebula evolution from its outer edge – ideally represented by comets – to its inner and warmer edge. Obviously this exploration asks for a detailed knowledge of the main constituents of the matter present in the different Solar System areas. Spectroscopy is a powerful tool to acquire this knowledge. We have participated with a large consortium of European researchers to the development of the Rosetta imaging spectrometer. We propose here to use our experience to develop a newly designed spectrometer to investigate the mineralogical composition of the Mercurial surface. Given the particular thermodynamical situation of the Mercurial surface, we have developed a concept that combines a medium IR low spectral resolution imager with a moderate spectral resolution NIR point spectrometer. The main goal of METHIS is to provide the mineralogical characterisation of the surface with sufficient spectral resolution in a scientifically diagnostic spectral range.     

Extraterrestrial organic chemistry: from the interstellar medium to the origins of life. Part 2: complex organic chemistry in the environment of planets and satellites.

During COSPAR'00 in Warsaw, Poland, in the frame of Sub-Commission F.3 events (Planetary Biology and Origins of Life), part of COSPAR Commission F (Life Sciences as Related to Space), and Commission B events (Space Studies of the Earth-Moon System, Planets, and Small Bodies of the Solar System) a large joint symposium (F.3.4/B0.8) was held on extraterrestrial organic chemistry. Part 2 of this symposium was devoted to complex organic chemistry in the environment of planets and satellites. The aim of this event was to cover and review new data which have been recently obtained and to give new insights on data which are expected in the near future to increase our knowledge of the complex organic chemistry occurring in several planets and satellites of the Solar System, outside the earth, and their implications for exobiology and life in the universe. The event was composed of two main parts. The first part was mainly devoted to the inner planets and Europa and the search for signatures of life or organics in those environments. The second part was related to the study of the outer solar system.     

Solar X-ray Monitor (XSM) on-board Chandrayaan-2 orbiter

The remote X-ray fluorescence spectroscopy is a powerful technique to investigate the elemental abundances in the atmosphere-less planetary bodies. The experiment involves measuring spectra of fluorescent X-rays from lunar surface using a low energy X-ray detector onboard an orbiting satellite. Since the flux of fluorescent X-ray lines critically depend on the flux and spectrum of the incident solar X-rays, it is essential to have simultaneous and accurate measurement of X-ray from both Moon and Sun. In the context of Moon, this technique has been employed since early days of space exploration to determine elemental composition of lunar surface. However, so far it has not been possible to exploit it to its full potential due to various reasons. Therefore it is planned to continue the remote X-ray fluorescence spectroscopy experiment on-board Chandrayaan-2 which includes both lunar X-ray observations and solar X-ray observations as two separate payloads. The lunar X-ray observations will be carried out by Chandra Large Area Soft x-ray Spectrometer (CLASS) experiment; whereas the solar X-ray observations will be carried out by a separate payload, Solar X-ray Monitor (XSM). Here we present the overall design of the XSM instrument, the present development status as well as preliminary results of the laboratory model testing. XSM instrument will have two packages namely – XSM sensor package and XSM electronics package. XSM will accurately measure spectrum of Solar X-rays in the energy range of 1–15 keV with energy resolution ∼200 eV @ 5.9 keV. This will be achieved by using state-of-the-art Silicon Drift Detector (SDD), which has a unique capability of maintaining high energy resolution at very high incident count rate expected from Solar X-rays. XSM onboard Chandrayaan-2 will be the first experiment to use such detector for Solar X-ray monitoring.     

HCN formation under electron impact: experimental studies and application to Neptune's atmosphere.

Laboratory experiments simulating organic synthesis in Neptune's atmosphere have been performed. We have submitted to a spark discharge gaseous mixtures containing 9 mbar of molecular nitrogen and 3 mbar of methane (the p(N2)/p(CH4) ratio is compatible with upper limits in Neptune's stratosphere) with varying quantities of molecular hydrogen. The spark discharge is used to model the energetic electrons produced by the impact of cosmic rays on the high atmosphere of Neptune. HCN is synthesized in the described experimental conditions, even with a low mixing ratio of molecular nitrogen. Studying the variation of HCN production with the initial composition of the gas mixture and extrapolating to high mixing ratio of molecular hydrogen allows to estimate HCN production in Neptune's atmosphere. The computed HCN production flux is 7x10(7) m-2 s-1, which is two orders of magnitude lower than the value predicted by chemical models for an internal source of N atoms. The major uncertainty in our extrapolation is the energetic distribution of electrons, implicitly assumed comparable in the discharge and in Neptune's atmosphere. We note that this distribution is also a source of uncertainty in chemical models. The chemical mechanism responsible for the local formation of HCN in the stratosphere probably occurs in the reactor too. We propose a simple characterization of the spark discharge. We thus link the molecular nitrogen dissociation cross section by electron impact to the measured parameters of the experiments (current, voltage, initial partial pressures) and to the resulting HCN partial pressures. However, other laboratory experiments with larger hydrogen pressures, requiring a more powerful electric source, have to be performed to yield a value of the cross section.     

The cometary contribution to prebiotic chemistry.

Different estimates based on dynamical considerations, lunar cratering rates, Solar System chemical abundances, and the single-impact theory on the origin of the Earth-Moon system suggest that comets and other related small, volatile-rich primitive minor bodies captured by the Earth during the early Archean must have been a major source of volatiles on our planet. It is likely that a substantial fraction of the organic molecules present in the colliding cometary nuclei, which may have included nitrogen bases and the precursors of amino acids, were destroyed due to the high temperatures and shock wave energy associated with the collision. However, the presence of H2O, CN, CH, CO, CO2 and other carbon-bearing molecules and radicals in the atmosphere of the Sun and in circumstellar shells around carbon-rich stars suggests that at least simple carbon species could have survived the cometary collisions. Under the anoxic conditions thought to prevail in the prebiotic terrestrial paleoatmosphere, the post-collisional formation of a large number of excited molecules and radicals, and the rapid quenching of the expanding gaseous ball may have led, upon rapid cooling, to the formation of molecules of biogenic elements and to their eventual deposition in localized environments where complex organic compounds of biochemical significance may have been produced and accumulated.     

HELIO: The Heliophysics Integrated Observatory

Heliophysics is a new research field that explores the Sun–Solar System Connection; it requires the joint exploitation of solar, heliospheric, magnetospheric and ionospheric observations.