Project Cassini: A Saturn Orbiter/Titan Probe mission proposal

Titan is the only moon in the solar system with a substantial atmosphere. The organic chemistry of its N₂–CH₄ atmosphere may resemble that of the earth's primitive atmosphere before life arose. The investigation of the synthesis of prebiotic molecules in Titan's atmosphere and the atmospheric and surface environments of this planet-sized moon will be the focal point of the Cassini Project proposed to the European Space Agency for an international Saturn Orbiter/Titan Probe mission.     

Question 2: Why an Astrobiological Study of Titan Will Help Us Understand the Origin of Life

For understanding the origin(s) of life on Earth it is essential to search for and study extraterrestrial environments where some of the processes which participated in the emergence of Life on our planet are still occurring. This is one of the goals of astrobiology. In that frame, the study of extraterrestrial organic matter is essential and is certainly not of limited interest regarding prebiotic molecular evolution. Titan, the largest satellite of Saturn and the only planetary body with an atmosphere similar to that of the Earth is one of the places of prime interest for these astrobiological questions. It presents many analogies with the primitive Earth, and is a prebiotic-like laboratory at the planetary scale, where a complex organic chemistry in is currently going on. Presented at: International School of Complexity – 4th Course: Basic Questions on the Origins of Life; “Ettore Majorana” Foundation and Centre for Scientific Culture, Erice, Italy, 1–6 October 2006.     

From exobiology to cosmobiology at LISA and elsewhere.

Since the emergence of Exobiology, back to the l960ties, this field drastically increased and, although differently named, is today a largely recognized scientific domain of wild interdisciplinarity. It includes not only the search for extraterrestrial living Systems, in particular by direct exploration of planetary bodies and studies of extraterrestrial materials, but also the study on the origins of life on Earth and, in connection to this field, the study of extraterrestrial organic chemistry. The exobiology programmes currently developed at LISA are related to this last aspect. They include the study of prebiotic-like chemistry in the gas and solid phases, based on laboratory simulation experiments, theoretical modeling and future in situ measurements in Titan's atmosphere and in cometary nuclei. A national program of exobiology, coordinated by LISA is under development in France, it covers many of the various aspects of Exobiology, including the study of life in extreme environments, as a reference tool for extraterrestrial life, the study of the primitive environment of the Earth, of the organic chemistry in comets and on Titan, of Mars and Europa and even of extrasolar planets as potential niches for extraterrestrial living systems, associated to the determination of the electromagnetic signatures of life. In parallel to this general program, a proposal for a large simulation chamber to be used as a national facility in particular to simulate the organic chemistry in various planetary environments, and in the interstellar medium, is under preparation. International cooperations linked to these programmes, in particular in the frame of the development of an exobiology facility on the International Space Station, would be of crucial interest.     

Review and Latest Results of Laboratory Investigations of Titan's Aerosols

Titan, the largest satellite of Saturn, has an atmosphere chiefly made up of N₂ and CH₄, and including many organics. This atmosphere also partly consists of hazes and aerosol particles which shroud the surface of this satellite, giving it a reddish appearance. The aerosols observed in Titan's atmosphere are thought to be synthesized at high altitudes (>300 km) and fall to the surface. Varying with temperature profiles, condensation phenomena take place in the lower atmosphere, about 100 km below. These solid particles, often called tholins, have been currently investigated for many years by laboratory scientists and physics modellers. This paper assesses past research and results in different fields (elemental composition, optical constants, pyrolysis, particle size), highlighting interests and questions aroused by these studies. It also presents the latest results and advances, and concludes with existing problems and future pathways.     

The atmosphere of Titan

Summary The discovery that Titan had an atmosphere was made by the identification of methane in the satellite's spectrum in 1944. But the abundance of this gas and the identification of other major constituents required the 1980 encounter by the Voyager 1 spacecraft. in the intervening years, traces of C₂H₂, C₂H₄, C₂H₆ and CH₃D had been posited to interpret emission bands in Titan's IR spectrum. The Voyager infrared Spectrometer confirmed that these gases were present and added seven more. The atmosphere is now known to be composed primarily of molecular nitrogen. But the derived mean molecular weight suggests the presence of a significant amount of some heavier gas, most probably argon. It is shown that this argon must be primordial, and that one can understand the evolution of Titan's atmosphere in terms of degassing of a mixed hydrate dominated by CH₄, N₂ and³⁶Ar. This model satisfactorily explains the absence of neon and makes no special requirements on the satellite's surface temperature. The organic chemistry taking place on Titan today invites comparision with chemical evolution on the primitive Earth prior to the origin of life.Adapted in commemoration of the many contributions of Harold Urey to the study of planetary atmospheres from an article in press in J Planet Sci (1982)     

Exobiology and the solar system: The CASSINI mission to Titan

The recent Voyager mission and the simulation experiments in the laboratory suggest that a complex nitrogen-organic chemistry is occuring at the periphery of Titan. Thus, this satel lite of Saturn appears as a privileged place in the solar system for the study of extraterrestrial organic chemistry which can be considered as part of Exobiology.Projects of space mission relating to Titan are already under investigation, in particular with the CASSINI proposal. The CASSINI project is a combination of a Saturn orbiter and a Titan probe mission. Such a mission would allow the first study in situ of a complex extraterrestrial organic chemistry in atmospheric phase.     

CHEMICAL EVOLUTION ON TITAN: COMPARISONS TO THE PREBIOTIC EARTH

Models for the origin of Titan's atmosphere, the processing of the atmosphere and surface and its exobiological role are reviewed. Titan has gained widespread acceptance in the origin of life field as a model for the types of evolutionary processes that could have occurred on prebiotic Earth. Both Titan and Earth possess significant atmospheres ( 1 atm) composed mainly of molecular nitrogen with smaller amounts of more reactive species. Both of these atmospheres are processed primarily by solar ultraviolet light with high energy particles interactions contributing to a lesser extent. The products of these reactions condense or are dissolved in other atmospheric species (aerosols/clouds) and fall to the surface. There these products may have been further processed on Titan and the primitive Earth by impacting comets and meteorites. While the low temperatures on Titan ( 72–180 K) preclude the presence of permanent liquid water on the surface, it has been suggested that tectonic activity or impacts by meteors and comets could produce liquid water pools on the surface for thousands of years. Hydrolysis and oligomerization reactions in these pools might form chemicals of prebiological significance. Other direct comparisons between the conditions on present day Titan and those proposed for prebiotic Earth are also presented.     

Organic syntheses from CH4−N2 atmospheres: Implications for Titan

Numerous experiments have already been performed, simulating the evolution of gaseous mixtures containing CH₄ when submitted to energy flux. From their results, it appears that a variety of organic compounds, including unsaturated hydrocarbons and nitriles such as HCN, can be synthesized into noticeable amounts from CH₄–N₂ mixtures. In particular, systematic studies of the influence of the composition of the mixture on the nature and amount of synthesized compounds show that organic volatile nitriles, and particularly cyanoacetylene and cyanogen, are formed only in media rich in nitrogen. Those nitriles have been identified very recently in the atmosphere of Titan, and thus, data from such laboratory experiments may provide important indirect information on the organic chemistry occuring at the periphery of this satellite of Saturn. However, during these experiments, there is a continuous formation and accumulation of molecular hydrogen, which does not occur in the atmosphere of Titan, because of H₂ escape. In order to reassess the data already available from this type of laboratory studies, experiments on CH₄–N₂ atmospheres, with and without H2 escape, have been recently performed. The influence of this parameter on the chemical evolution of the atmosphere and on the nature and relative quantities of organic compounds has been studied.After reviewing these experiments, implications of the obtained results on the organic chemistry at the periphery of Titan are discussed.Paper presented at the 6th College Park Colloquium, October 1981.     

Heteropolypeptides on Titan?

Since hydrogen cyanide is a component of Titan's hazy atmosphere, HCN polymers might also be present by way of a low energy pathway leading initially to the synthesis of polyaminomalonitrile. Subsequent reactions of HCN with the activated nitrile groups of this HCN homopolymer would then yield heteropolyamidines, readily converted to heteropolypeptides following contact with frozen water on the surface of Titan.Similar HCN polymers in the reducing atmospheres of Jupiter and Saturn could be major contributors to the yellow-brown-orange appearance of these giant planets.Any detection of such HCN chemistry by the Voyager missions or the pending Galileo probe would constitute evidence for the hypothesis that heteropolypeptides on the primitive Earth were synthesized directly from hydrogen cyanide and water without the intervening formation of -amino acids.Paper presented at the 6th College Park Colloquium, October 1981.     

Prebiotic processes in planetary atmospheres

Within 40 years of experimental studies in prebiotic chemistry, most of the building blocks of the living systems have been synthesized in plausible conditions of the primitive Earth. The starting ingredients correspond to two complementary classes: volatile organics, and their non volatile oligomers. They may have been formed in the atmosphere on the primitive Earth and/or imported by extra-terrestrial sources. Organic chemistry is involved in meteorites, comets, in the giant planets and several of their satellites. Again this chemistry presents the two complementary aspects. In particular, with a dense reduced atmosphere rich in organic compounds in gas and aerosol phases, Titan appears as a natural laboratory for studying prebiotic chemistry at a planetary scale.     

The outer solar system: Perspectives for exobiology

The outer solar system contains many environments of interest for studies of the origin of life. Recent observations support the idea that Jupiter and Saturn have retained the mixture of elements originally present in the solar nebula. Subsequent low temperature chemistry has produced the expected array of simple molecules giving characteristic absorption bands in the spectra of these planets. Microwave and infrared observations show that the lower atmospheres are at temperatures above 300 K. Sources of energy for non-equilibrium chemistry seem available at least on Jupiter and the presence of an array of colored materials in the Jovian cloud belts has often been cited as evidence for the existence of complex abiogenic organic molecules. Further study of both planets in an exobiological context seems well worthwhile; potentially productive methods of investigation (including planned space missions) can be described and evaluated from this point of view. Uranus and Neptune are clearly deficient in light gases, but otherwise little is known with certainty about these distant planets. Again unusually high temperatures have been reported, but not above 273 K. Pluto and many of the outer planet satellites appear to represent a class of small bodies very unlike our neighbors in the inner solar system. Titan, Saturn's largest satellite, is especially interesting for our purposes because of its atmosphere. Methane and hydrogen are both present, and Titan's unusually reddish color again suggests the presence of organic compounds. The hydrogen-methane ratio is likely to be more similar to that of a primitive reducing terrestrial atmosphere than the ratios for Jupiter and Saturn, suggesting that in some respects this satellite may provide an even better model for early organic synthesis on the Earth. The problem of Titan's heat balance and atmospheric composition are currently under active investigation.     

Physical conditions on the early Earth

The formation of the Earth as a planet was a large stochastic process in which the rapid assembly of asteroidal-to-Mars-sized bodies was followed by a more extended period of growth through collisions of these objects, facilitated by the gravitational perturbations associated with Jupiter. The Earth's inventory of water and organic molecules may have come from diverse sources, not more than 10% roughly from comets, the rest from asteroidal precursors to chondritic bodies and possibly objects near Earth's orbit for which no representative class of meteorites exists today in laboratory collections. The final assembly of the Earth included a catastrophic impact with a Mars-sized body, ejecting mantle and crustal material to form the Moon, and also devolatilizing part of the Earth. A magma ocean and steam atmosphere (possibly with silica vapour) existed briefly in this period, but terrestrial surface waters were below the critical point within 100 million years after Earth's formation, and liquid water existed continuously on the surface within a few hundred million years. Organic material delivered by comets and asteroids would have survived, in part, this violent early period, but frequent impacts of remaining debris probably prevented the continuous habitability of the Earth for one to several hundred million years. Planetary analogues to or records of this early time when life began include Io (heat flow), Titan (organic chemistry) and Venus (remnant early granites).     

Formation of organic compounds from simulated Titan atmosphere: perspectives of the Cassini mission.

Gas mixtures of methane and nitrogen were subjected to proton irradiation (PI), gamma irradiation (GI), UV irradiation (UV) or spark discharges (SD), and the products were analyzed to compare possible energy sources for synthesis of organics in Titan. SD mainly gave unsaturated hydrocarbons, while PI gave saturated hydrocarbons. N-containing organics were detected in PI, GI and SD, but not in UV. The formers yielded amino acids after acid-hydrolysis of solid phase products (tholin). Comparison of the present results with those by Cassini-Huygens [correction of Heygens] mission will make it possible to prove major energy sources for organic synthesis in Titan atmosphere.     

Gas-Phase Reactions in Extraterrestrial Environments: Laboratory Investigations by Crossed Molecular Beams

We have investigated gas-phase reactions of N(²D) with the most abundant hydrocarbons in the atmosphere of Titan by the crossed molecular beam technique. In all cases, molecular products containing a novel CN bond are formed, thus suggesting possible routes of formation of gas-phase nitriles in the atmosphere of Titan and primordial Earth. The same approach has been recently extended to the study of radical–radical reactions, such as the reaction of atomic oxygen with the CH₃ and C₃H₅ radicals. Products other than those already considered in the modeling of planetary atmospheres and interstellar medium have been identified. Presented at: National Workshop On Astrobiology: Search For Life In The Solar System, Capri, Italy, 26 to 28 October, 2005.     

Dark matter in the solar system: Hydrogen cyanide polymers

In the presence of a base such as ammonia liquid HCN (bp 25 °C) polymerizes readily to a black solid from which a yellow-brown powder can be extracted by water and further hydrolyzed to yield-amino acids. These macromolecules could be major components of the dark matter observed on many bodies in the outer solar system. The non-volatile black crust of comet Halley, for example, may consist largely of such polymers, since the original presence on cometary nuclei of frozen volatiles such as methane, ammonia, and water makes them possible sites for the formation and condensed-phase polymerization of hydrogen cyanide. It seems likely, too, that HCN polymers are among the dark —CN bearing solids identified spectroscopically by Cruikshanket al. in the dust of some other comets, on the surfaces of several asteroids of spectral class D, within the rings of Uranus, and covering the dark hemisphere of Saturn's satellite Iapetus. HCN polymerization could account also for the yellow-orange-brown coloration of Jupiter and Saturn, as well as for the orange haze high in Titan's atmosphere. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers through cometary bombardment or terrestrial synthesis, producing a proteinaceous matrix that promoted the molecular interactions leading to the emergence of life.     

Corona chemistry in Titan.

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 charged particles leads to corona discharges which are characterized by low current densities. 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-butane, 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 a highly branched hydrocarbon deposit. We present the trends of hydrocarbons and nitriles formation as a function of discharge time in an ample interval and have derived their initial yields of formation. The 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 too low by a factor of 10 to 40. While some ethene will be produced by charged-particle chemistry, the production of ethene by corona processes and its 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.     

Planetary Organic Chemistry and the Origins of Biomolecules

Organic chemistry on a planetary scale is likely to have transformed carbon dioxide and reduced carbon species delivered to an accreting Earth. According to various models for the origin of life on Earth, biological molecules that jump-started Darwinian evolution arose via this planetary chemistry. The grandest of these models assumes that ribonucleic acid (RNA) arose prebiotically, together with components for compartments that held it and a primitive metabolism that nourished it. Unfortunately, it has been challenging to identify possible prebiotic chemistry that might have created RNA. Organic molecules, given energy, have a well-known propensity to form multiple products, sometimes referred to collectively as “tar” or “tholin.” These mixtures appear to be unsuited to support Darwinian processes, and certainly have never been observed to spontaneously yield a homochiral genetic polymer. To date, proposed solutions to this challenge either involve too much direct human intervention to satisfy many in the community, or generate molecules that are unreactive “dead ends” under standard conditions of temperature and pressure. Carbohydrates, organic species having carbon, hydrogen, and oxygen atoms in a ratio of 1:2:1 and an aldehyde or ketone group, conspicuously embody this challenge. They are components of RNA and their reactivity can support both interesting spontaneous chemistry as part of a “carbohydrate world,” but they also easily form mixtures, polymers and tars. We describe here the latest thoughts on how on this challenge, focusing on how it might be resolved using minerals containing borate, silicate, and molybdate, inter alia.Interesting organic chemistry occurs throughout the cosmos, including in presolar nebulae (see the article in this collection by Pascale Erhrenfreund), asteroidal bodies (see the article in this collection by Sandra Pizzarello) and icy bodies near the outer boundary of our solar system (Bernstein et al. 2002). Although organic molecules made in off-Earth locales almost certainly contributed to the reduced carbon inventory on Earth before life emerged, planetary processing on Earth undoubtedly also contributed to the inventory of prebiotic molecules that were available to life as it originated (assuming that Earth was the site of life''s origin). Indeed, in the RNA first model for the origin of life on Earth (Joyce and Orgel 1999)(Benner 2009), it is often proposed that terran-based chemistry produced RNA in oligomeric form to initiate Darwinian evolution.How are we to constrain models for planetary processing to converge on a model for what actually happened on Earth four billion years ago? Today, atmospheric dioxygen (O₂) readily converts organic materials to carbon dioxide, making it essentially impossible to observe such processing on the surface of Earth. Furthermore, the ubiquity of life on modern Earth means that any organic processing is more likely to reflect biology than prebiology. The closest we may come today to observe organic transformations absent biology on a planetary scale might be on Titan, a moon of Saturn whose atmosphere and surface is rich in reduced carbon.Nevertheless, it is possible to apply a general understanding of organic chemical reactivity to suggest chemical reactions that might have occurred on early Earth and the products that they might have produced. These suggestions are constrained by models for the atmosphere and mineralogy of early Earth, although these constraints might change as models improve.In this article, we assume that the atmosphere of early Earth was less oxidizing than today''s atmosphere, although not as rich in methane as the simulated atmosphere used in the classic experiments of Stanley Miller (Miller 1955). Further, we assume that the atmosphere on early Earth had access to many sources of energy. These include electrical discharge, ultraviolet and visible light (although the Sun was almost certainly dimmer then than now, a Titan-like haze may have prevented high energy photons from reacting the Earth''s surface), volcanism (providing not only heat but also reactive species and mixtures not at thermodynamic equilibrium), ionizing radiation, and impacts. (See Pizzarello and Shock 2010 for a discussion of such energy sources.)We also assume that life emerged after the planet underwent a geological fractionation in which heavier minerals and elemental iron sank towards the core, leaving lighter rocks to form the crust. Open questions concern the inventory of water relative to the surface of early Earth, an inventory that determined whether planetary organic transformations might have occurred on dry land or below water on a planetary surface that was totally submerged.     

Bridging the gap between microbial limits and extremes in space: space microbial biotechnology in the next 15 years

The establishment of a permanent human settlement in space is one of humanity’s ambitions. To achieve this, microorganisms will be used to carry out many functions such as recycling, food and pharmaceutical production, mining and other processes. However, the physical and chemical extremes in all locations beyond Earth exceed known growth limits of microbial life. Making microbes more tolerant of a greater range of extraterrestrial extremes will not produce organisms that can grow in unmodified extraterrestrial environments since in many of them not even liquid water can exist. However, by narrowing the gap, the engineering demands on bioindustrial processes can be reduced and greater robustness can be incorporated into the biological component. I identify and describe these required microbial biotechnological modifications and speculate on long-term possibilities such as microbial biotechnology on Saturn’s moon Titan to support a human presence in the outer Solar System and bioprocessing of asteroids. A challenge for space microbial biotechnology in the coming decades is to narrow the microbial gap by systemically identifying the genes required to do this and incorporating them into microbial systems that can be used to carry out bioindustrial processes of interest.     

Thermal Energy and the Origin of Life

Life has evolved on Earth with electromagnetic radiation (light), fermentable organic molecules, and oxidizable chemicals as sources of energy. Biological use of thermal energy has not been observed although heat, and the thermal gradients required to convert it into free energy, are ubiquitous and were even more abundant at the time of the origin of life on Earth. Nevertheless, Earth-organisms sense thermal energy, and in suitable environments may have gained the capability to use it as energy source. It has been proposed that the first organisms obtained their energy by a first protein named pF₁ that worked on a thermal variation of the binding change mechanism of today's ATP sythase enzyme. Organisms using thermosynthesis may still live where light or chemical energy sources are not available. Possible suitable examples are subsurface environments on Earth and in the outer Solar System, in particular the subsurface oceans of the icy satellites of Jupiter and Saturn.     

Automated life-detection experiments for the Viking mission to Mars

As part of the Viking mission to Mars in 1975, an automated set of instruments is being built to test for the presence of metabolizing organisms on that planet. Three separate modules are combined in this instrument so that samples of the Martian surface can be subjected to a broad array of experimental conditions so as to measure biological activity. The first, the Pyrolytic Release Module, will expose surface samples to a mixture of C¹⁴O and C¹⁴O₂ in the presence of Martian atmosphere and a light source that simulates the Martian visible spectrum. The assay system is designed to determine the extent of assimilation of CO or CO₂ into organic compounds. A small amount of water can be injected into the gas phase during incubation upon command. The Gas Exchange Module will incubate surface samples in a humidified CO₂ atmosphere. At specified times, portions of the incubation atmosphere will be analyzed by gas chromatography to detect the release or uptake of CO₂ and several additional gases. A rich and diversified source of organic nutrients and trace compounds will be available as further additions to the incubating samples. The Label Release Module will incubate surface samples with a dilute aqueous solution of simple radioactive organic substrates in Martian atmosphere, and the gas phase will be monitored continuously for the release of labeled CO₂. Each module, in addition to its gas and nutrient sources, incubation chambers, and detector systems, contains heaters capable of sterilizing surface samples to serve as controls. Since the instrument is designed to operate under Martian conditions and to detect Martian, not terrestrial, organisms, and because the final flight instruments can perform only four assays for each module, formidable problems exist in testing the hardware. The implications of this situation are discussed.