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.     

Surface-atmosphere interactions on Titan compared with those on the pre-biotic Earth.

The surface and atmosphere of Titan constitute a system which is potentially as complex as that of the Earth, with the possibility of precipitation, surface erosion due to liquids, chemistry in large surface or subsurface hydrocarbon reservoirs, surface expressions of internal activity, and occasional major impacts leading to crustal melting. While none of the above have been observed as yet, the composition, density and thermal properties of Titan's atmosphere make it uniquely suited in the outer solar system as a place where such processes may occur. The one attribute of the Earth not expected on Titan is biological activity, which has had a profound effect on the evolution of the Earth's surface-atmosphere system. The earliest environment of Titan could have been warm enough for liquid ammonia-water solutions to exist on or near surface; pre-biotic organic processes may have taken place in such an environment. After a few hundred million years surface ammonia-water would have disappeared. Therefore, study of Titan through the Cassini-Huygens mission, planned for launch in 1997, primarily affords the opportunity to understand planet-wide surface-atmosphere interactions in the presence of fluids but in the absence of life. More speculative is the possibility that endogenic and exogenic heating continue to provide short-lived environments on Titan wherein pre-biotic organic processes in the presence of water happen.     

An aerobot for global in situ exploration of Titan

This paper describes the design and component testing of an aerobot that would be capable of global in situ exploration of Saturn’s moon, Titan, over a 6–12 month mission lifetime. The proposed aerobot is a propeller-driven, buoyant vehicle that resembles terrestrial airships. However, the extremely cold Titan environment requires the use of cryogenic materials of construction and careful thermal design for protection of temperature-sensitive payload elements. Multiple candidate balloon materials have been identified based on extensive laboratory testing at 77 K. The most promising materials to date are laminates comprised of polyester fabrics and/or films with areal densities in the range of 40–100 g/m². The aerobot hull is a streamlined ellipsoid 14 m in length with a maximum diameter of 3 m. The enclosed volume of 60 m³ is sufficient to float a mass of 234 kg at a maximum altitude of 8 km at Titan. Forward and aft ballonets are located inside the hull to enable the aerobot to descend to the surface while preserving a fully inflated streamlined shape. Altitude changes are effected primarily through thrust vectoring of the twin main propellers, with pressure modulated buoyancy change via the ballonets available as a slower backup option. A total of 100 W of electrical power is provided to the vehicle by a radioisotope power supply. Up to half of this power is available to the propulsion system to generate a top flight speed in the range of 1–2 m/s. This speed is expected to be greater than the near surface winds at Titan, enabling the aerobot to fly to and hover over targets of interest. A preliminary science payload has been devised for the aerobot to give it the capability for aerial imaging of the surface, atmospheric observations and sampling, and surface sample acquisition and analysis. Targeting, hovering, surface sample acquisition and vehicle health monitoring and automatic safing actions will all require significant on-board autonomy due to the over 2 h round trip light time between Titan and Earth. An autonomy architecture and a core set of perception, reasoning and control technologies is under development using a free-flying airship testbed of approximately the same size as the proposed Titan aerobot. Data volume from the Titan science mission is expected to be on the order of 100–300 Mbit per day transmitted either direct to Earth through an 0.8 m high gain antenna or via an orbiter relay using an omni-directional antenna on the aerobot.     

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.     

Experimental results for Titan aerobot thermo-mechanical subsystem development

This paper describes experimental results from a development program focused on maturing Titan aerobot technology in the areas of mechanical and thermal subsystems. Results from four key activities are described: first, a cryogenic balloon materials development program involving coupon and cylinder tests and culminating in the fabrication and testing of an inflated 4.6 m long prototype blimp at 93 K; second, a combined lab experiment and numerical simulation effort to assess potential problems resulting from radioisotope power source waste heat generation near an inflated blimp; third, an aerial deployment and inflation development program consisting of laboratory and helicopter drop tests on a near full scale (11 m long) prototype blimp; and fourth, a proof of concept experiment demonstrating the viability of using a mechanically steerable high gain antenna on a floating blimp to perform direct to Earth telecommunications from Titan. The paper provides details on all of these successful activities and discusses their impact on the overall effort to produce mature systems technology for future Titan aerobot missions.     

The atmospheric greenhouse effect and climates on various planets

The greenhouse effect of the planetary atmospheres is considered and its evolution as a result of variations in the chemical composition and in gas abundances of the atmospheres as well as in the chemical composition, size distribution and concentration of aerosol components. A computer modelling gave the values of the greenhouse effect of the atmospheres of the Earth, Mars, Venus, Jupiter, and Titan. It is shown that the atmospheric greenhouse effect plays a decisive role in the formation of the planetary climates and that it has substantially changed in the process of the planetary evolution. The greenhouse effect mechanism has always been and still is a major factor of the mean global planetary climate.     

Formation of bioorganic compounds in simulated planetary atmospheres by high energy particles or photons.

Various types of organic compounds have been detected in Jupiter, Titan, and cometary coma. It is probable that organic compounds were formed in primitive Earth and Mars atmospheres. Cosmic rays and solar UV are believed to be two major energy sources for organic formation in space. We examined energetics of organic formation in simulated planetary atmospheres. Gas mixtures including a C-source (carbon monoxide or methane) and a N-source (nitrogen or ammonia) was irradiated with the followings: High energy protons or electrons from accelerators, gamma-rays from 60Co, UV light from a deuterium lamp, and soft X-rays or UV light from an electron synchrotron. Amino acids were detected in the products of particles, gamma-rays and soft X-rays irradiation from each gas mixture examined. UV light gave, however, no amino acid precursors in the gas mixture of carbon monoxide, nitrogen and nitrogen. It gave only a trace of them in the gas mixture of carbon monoxide, ammonia and water or that of methane, nitrogen and water. Yield of amino acid precursors by photons greatly depended on their wavelength. These results suggest that nitrogen-containing organic compounds like amino acid precursors were formed chiefly with high energy particles, not UV photons, in Titan or primitive Earth/Mars atmospheres where ammonia is not available as a predominant N-source.     

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.     

A facility for simulating Titan’s environment

As a result of measurements acquired by the Cassini–Huygens mission of Titan’s near surface atmospheric composition and temperature, Titan conditions can now be simulated in the laboratory and samples can subsequently be subjected to those conditions. Titan demonstrates an active hydrological-like cycle with its thick atmosphere, dynamic clouds, polar lakes of methane and ethane, moist regolith, and extensive fluvial erosive features. Unlike Earth, Titan’s hydrological-like cycle likely involves several constituents, primarily methane and ethane. Here the properties of a new Titan simulation facility are presented, including conceptual methodology, design, implementation, and performance results. The chamber maintains Titan’s surface temperature and pressure, and the sample cryogenic liquids undergoing experimentation are condensed within the chamber itself. During the experiments, the evaporation rates of the sample liquids are directly determined by continually measuring mass. Constituents are analyzed utilizing a Fourier Transform Infrared Spectroscopy (FTIR), and vapor concentrations are determined using a gas chromatograph fitted with a Flame Ionization Detector (FID). All pertinent data is logged via computer. Under laboratory conditions, the direct measurements of the evaporation rates of methane, ethane, and mixtures thereof can be achieved. Among the processes to be studied are the effects of regolith on transport from the subsurface to the atmosphere, the freezing point depression effects of dissolved nitrogen, and the solubility of various relevant organic compounds.     

An engineering model of Titan surface winds for Dragonfly landed operations

Winds near the ground on Titan for the Dragonfly landing site (near Selk crater, 10°N) for the mid-2030s (Titan late southern summer, L_s ~ 310°) are estimated for mission design purposes. Prevailing winds due to the global circulation are typically 0.5 m/s, and do not exceed 1 m/s. Local terrain-induced flows such as slope winds appear to be similarly capped at 1 m/s. At various landing sites and times, these two contributions will vectorially combine to yield steady winds (for part of a Titan day, Tsol) of up to 2.0 m/s, but typically less – the slope wind component will be small in the mid-morning. In early afternoon, as on Earth and Mars, solar-driven convection in the planetary boundary layer will cause wind fluctuations of the order of 0.1 m/s, varying with a typical timescale of ~1000 s. Occasionally this convection organizes into coherent ‘dust devil’ vortices: detectable vortices with speeds of 1 m/s are predicted about once per Titan day. We have introduced the convective velocity scale combined with the advection time of PBL cells as a metric to derive the frequency of occurrence of gusts associated with convective vortices (‘dust devils’). Maximum possible vortex winds on Titan of 2.8 m/s may be expected only once per 40 Tsols, and define the maximum wind (4.8 m/s at 10 m height) that Dragonfly must tolerate without damage. The applicability of different wind combinations, scaled to the height of relevant Dragonfly components above the ground (e.g. the maximum corresponds to 3.9 m/s at 1.3 m height) by a logarithmic wind profile, to Dragonfly design and operations are discussed.     

Life in the solar system.

Life, defined as a chemical system capable of transferring its molecular information via self-replication and also capable of evolving, must develop within a liquid to take advantage of the diffusion of complex molecules. On Earth, life probably originated from the evolution of reduced organic molecules in liquid water. Organic matter might have been formed in the primitive Earth's atmosphere or near hydrothermal vents. A large fraction of prebiotic organic molecules might have been brought by extraterrestrial-meteoritic and cometary dust grains decelerated by the atmosphere. Any celestial body harboring permanent liquid water may therefore accumulate the ingredients that generated life on the primitive Earth. The possibility that life might have evolved on early Mars when water existed on the surface marks it as a prime candidate in a search for bacterial life beyond the Earth. Europa has an icy carapace. However, cryovolcanic flows at the surface point to a possible water subsurface region which might harbor a basic life form. The atmosphere and surface components of Titan are also of interest to exobiology for insight into a hydrocarbon-rich chemically evolving world. One-handed complex molecules and preferential isotopic fractionation of carbon, common to all terrestrial life forms, can be used as basic indicators when searching for life beyond the Earth.     

Chemical evolution and the origin of life.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.     

Chemical evolution of primitive solar system bodies.

In this paper we summarize some of the most salient observations made recently on the organic molecules and other compounds of the biogenic elements present in the interstellar medium and in the primitive bodies of the solar system. They include the discovery of the first phosphorus molecular species in dense interstellar clouds, the presence of complex organic ions in the dust and gas phase of Halley's coma, the finding of unusual, probably presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites, and new developments on the chemical evolution of Titan, the primitive Earth, and early Mars. Some of the outstanding problems concerning the synthesis of organic molecules on different cosmic bodies are also discussed from an exobiological perspective.     

Unusually strong magnetic fields in Titan’s ionosphere: T42 case study

Observations of unusually large magnetic fields in the ionosphere indicate periods of maximum stress on Titan’s ionosphere and potentially of the strongest loss rates of ionospheric plasma. During Titan flyby T42, the observed magnetic field attained a maximum value of 37 nT between an altitude of 1200 and 1600 km, about 20 nT stronger than on any other Titan pass and close to five times greater in magnetic pressure. The strong fields occurred near the corotation-flow terminator rather than at the sub-flow point, suggesting that the flow which magnetized the ionosphere was from a direction far from corotation and possibly towards Saturn. Extrapolation of solar wind plasma conditions from Earth to Saturn using the University of Michigan MHD code predicts an enhanced solar wind dynamic pressure at Saturn close to this time. Cassini’s earlier exits from Saturn’s magnetosphere support this prediction because the Cassini Plasma Spectrometer instrument saw a magnetopause crossing three hours before the strong field observation. Thus it appears that Titan’s ionosphere was magnetized when the enhanced solar wind dynamic pressure compressed the Saturnian magnetosphere, and perhaps the magnetosheath magnetic field, against Titan. The solar wind pressure then decreased, leaving a strong fossil field in the ionosphere. When observed, this strong magnetic flux tube had begun to twist, further enhancing its strength.     

Analytical pyrolysis experiments of Titan aerosol analogues in preparation for the Cassini Huygens mission.

Comparative pyrolysis mass spectrometric data of Titan aerosol analogues, called "tholins", are presented. The Titan tholins were produced in the laboratory at Cornell by irradiation of simulated Titan atmospheres with high energy electrons in plasma discharge. Mass-spectrometry measurements were performed at FOM of the solid phase of various tholins by Curie-point pyrolysis Gas-Chromatography/Mass-Spectrometry (GCMS) and by temperature resolved in source Pyrolysis Mass-Spectrometry to reveal the composition and evolution temperature of the dissociation products. The results presented here are used to further define the ACP (Aerosol Collector Pyrolyser)-GCMS experiment and provide a basis for modelling of aerosol composition on Titan and for the interpretation of Titan atmosphere data from the Huygens probe in the future.     

The physical nature of Titan's aerosols: laboratory simulations.

The atmosphere of Titan is known to contain aerosols, as evidenced by the Voyager observations of at least three haze layers. Such aerosols can have significant effects on the reflection spectrum of Titan and on the chemistry and thermal structure of its atmosphere. To investigate some of these effects, laboratory simulations of the chemistry of Titan's atmosphere have been done. The results of these studies show that photolysis of acetylene, ethylene, and hydrogen cyanide, known constituents of Titan's atmosphere, yields sub-micron sized spheres, with mean diameters ranging from 0.4 to 0.8 microns, depending on the pressures of the reactant gases. Most of the spheres are contained in near-linear aggregates. The formation of the aggregates is consistent with models of Titan's reflection spectrum and polarization, which are best fit with non-spherical particles. At room temperature, the particles are very sticky, but their properties at low temperatures on Titan are presently not known.     

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.     

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

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

Space station gas-grain simulation facility: Application to exobiology

The Space Station provides an environment in which the forces required to suspend particles during an experiment can be reduced by as much as six orders of magnitude. This reduction in levitation force enables us to perform many new experiments in a variety of disciplines. We have grouped these experiments into two catatgories: 1) those involving an individual particle or the interaction between a few particles and 2) those involving clouds of particles. We consider only particle experiments at this stage because cloud experiments suffer from electrostatic interactions and levitation-forced coalescence therefore requiring considerably more space, mass and crew interaction. The displacement of a particle resulting from g-jitter for ballistic, Knudsen and Stokes flow regimes is considered in detail and the radiation, acoustic, electrostatic and electromagnetic levitation mechanisms to control this motion are reviewed. We have selected the simulation of organic haze production on Titan as an example experiment for detailed study. The objective of this experiment is to simulate the photolysis of methane and the subsequent formation of the organic haze particles in the upper atmosphere of Titan.