Cyclic octatomic sulfur: a possible infrared and visible chromophore in the clouds of jupiter.

A brown polymeric material, produced under simulated Jovian conditions, is composed primarily of cyclic octatomic sulfur, although a range of complex organic compounds is also present. The polymeric sulfur, produced from the ultraviolet photolysis of hydrogen sulfide, exhibits its strongest band at 465 reciprocal centimeters, in fair agreement with the frequency of the unidentified Jovian absorber recently announced by Houck et al. Polymeric octatomic sulfur may be an important constituent of the Jovian clouds.

Long-wavelength ultraviolet photoproduction of amino acids on the primitive Earth.

Amino acids are produced under possible primitive Earth conditions by irradiation of gas mixtures with long-wavelength ultraviolet light, representing the most abundant useful energy source for prebiological organic synthesis. Hydrogen sulfide is the initial photon acceptor in this work; superthermal atomic hydrogen photodissociation products appear to initiate reactions leading to amino acid synthesis with an overall quantum yield on the order of 5X10(-5).

Ultraviolet-photoproduced organic solids synthesized under simulated jovian conditions: molecular analysis.

In an earlier paper, Khare and Sagan reported the production of a brownish polymeric material from the near-ultraviolet irradiation of simulated jovian atmospheres with a low hydrogen abundance. Examination of this product indicates that hydrogen sulfide is the initial photon acceptor; the powder resulting after extraction with benzene is 84 percent sulfur, largely S(8). In results reported here, the remaining 16 percent was pyrolyzed and then examined by gas chromatography-mass spectrometry. Pyrolysis at 450 degrees C yielded a series of alkanes, alkenes, C(3)-alkylbenzenes, aromatics, thiophenes, alkylthiophenes, alkylmercaptans, alkyldisulfides, together with the nitrogenous compounds hydrogen cyanide, methyl cyanide, alkylisothiocyanates, acrylonitrile, and allylisothiocyanates. Some of these compounds might be sought on Jupiter and Saturn and their satellites by remote infrared and ultraviolet spectroscopy and directly by entry probes.

Triton: stratospheric molecules and organic sediments.

Hydrocarbons and nitriles are produced in Triton's stratosphere by energetic electrons from Neptune's magnetosphere and other charged particle sources. Laboratory plasma experiments reported here show a substantial yield of molecules from low pressure flows of 10(-3) CH4 in N2 appropriate to Triton if both CH4 and N2 are saturated at the surface. An active magnetosphere similar to that of Uranus would result in a flux approximately 0.3 erg cm-2 s-1 of 0.1-1 MeV electrons in Triton's stratosphere; molecular production rates are then 10(6)-10(8) cm-2 s-1 for NH3, C2H2, HCN, and NCCN; tens of hundreds of gm cm-2 of these compounds per 10(9) yr (and lesser quantities of at least eight other molecules experimentally detected) would freeze to fine-grained white condensates in the lower stratosphere and sediment to the surface. Along with dark/colored organic haze produced in the stratosphere and other heteropolymers produced at the surface, these condensates are subjects to redistribution by aeolian processes and may appear as lag deposits and/or sediment layers. A simple eddy diffusion model indicates abundances approximately 10(19) molec cm-2 for HCN and C2H2, and > 10(17) molec cm-2 for NCCN, CH3CCH, CH2CCH2, and CH3CN in the stratosphere; these and other organic molecules will be detectable by IRIS if the stratosphere is (as expected) heated through ultraviolet and visible light absorption by the haze.

Coloration and darkening of methane clathrate and other ices by charged particle irradiation: applications to the outer solar system.

Methane clathrate is expected to be an important carbon-containing ice in the outer solar system. We investigate the effect of electron irradiation by coronal discharge on several simple hydrocarbons enclathrated in or mixed with H2O or H2O+NH3 in simulation of the effects of the solar wind, planetary magnetospheric particles, and cosmic rays on surfaces containing these ices in the outer solar system and interstellar space. H2O+CH4 clathrate, H2O+C2H6, H2O+CH4+NH3, H2O+C2H6+NH3, and H2O+C2H2 are all initially white ices, and all produce yellowish to brownish organic products upon charged particles irradiation. Significant coloration occurs with doses of 10(9) erg cm-2, corresponding to short interplanetary irradiation times. Uranian magnetospheric electrons penetrate to approximately 1 mm depth and deposit this dose in 8, 30, 65, 200, and 500 years into the surfaces of Miranda, Ariel, Umbriel, Titania, and Oberon, respectively. Further irradiation of the laboratory ice surface results in a progressive darkening and a more subdued color. For a conversion efficiency to solids G approximately equal to 1 molecule keV-1, the upper limit for the time for total destruction of CH4 and other simple hydrocarbons in the upper 1 mm is 5 x 10(4) years (Miranda) to 3 x 10(6) years (Oberon). Remote detection of CH4 is possible only when its replenishment rate exceeds the destruction rate at the depth probed by spectroscopy. Reflection spectroscopy or irradiated H2O+CH4 frost is compared with the spectra of several outer solar system objects and to other relevant organic and inorganic materials. Ultraviolet-visible and infrared transmission spectroscopy of the postirradiation residues is presented. Persistence of color and of CH4 ice bands on Triton and Pluto suggests ongoing surface activity and/or atmospheric haze. Over 4 x 10(9) year time scales, > or = 10 m of satellite and cometary surface material is processed by cosmic rays to a radiation-hardened ice-tholin mixture devoid of CH4. Preaccretional chemistry, exogenous materials, and endogenous organic chemistry all contribute to the spectral properties of icy satellites which accreted simple CH(O) molecules. Radiation darkening traces the deposition of mobilized or impact-exposed carbon-bearing volatiles on these satellites. More exhaustive experiments are necessary to work out the detailed relationships between initial composition, exposure age, and color/albedo.

Solid hydrocarbon aerosols produced in simulated Uranian and Neptunian stratospheres.

Optical constants n and k are measured for thin hydrocarbon films produced from charged particles (RF plasma) irradiation of (1) 100% CH4; (2) 7% CH4, 93% H2; (3) 0.5% CH4, 99.5% H2; (4) 0.0002% CH4, 99.3% H2 (with impurities); and (5) 3 to 25% CH4, 25% He, remainder H2--all at submillibar pressures. In all experiments, yellow to deep brown-red solid products are synthesized which are hypothesized to be, at least in part, the unidentified visible and near-UV chromophores in the stratospheres of Uranus and Neptune. Results for experiments 2, 3, and 4 are in good mutual accord, but are significantly different from experiments 1 and 5. He in the precursor gases affects the product composition. Typical solid products for experiments 5 show, at 0.55 micrometer wavelength, n = 1.60 +/- 0.05, 3 x 10(-2) > or = k > or = 3 x 10(-3), and [C/H] approximately equal to 0.7. These results are, for n and k respectively, consistent with and in excellent agreement with those derived from high phase angle Voyager 2 photometry of Uranus (Pollack et al., this issue). Aerosols produced directly from the atmosphere by precipitating magnetospheric charged particles may be competitive with those produced by UV and charged particle irradiation of simple hydrocarbon condensates. The optical and chemical properties of aerosols in the Uranian and Neptunian atmospheres may evolve toward higher values of n and k and higher carbon content as the particles sediment through changing radiation and thermal environments.

Light hydrocarbons from plasma discharge in H2-He-CH4: first results and Uranian auroral chemistry.

Voyager 2 found that the Uranian magnetosphere has a substantial flux of energetic charged particles, which becomes rich in higher energies at low magnetospheric L near the orbit of Miranda. The electrons precipitate to produce aurorae, which have been observed in the ultraviolet. The more energetic component of the precipitating electrons can initiate radiation chemistry in the methane-poor stratosphere, near 0.1 mbar where the CH4 mole fraction XCH4 approximately equal to 10(-5). We present laboratory results for cold plasma (glow) discharge in continuous flow H2-He-CH4 atmospheres with mol fractions XCH4 = 10(-2) to 10(-3) and total pressure p = 60 to 0.6 mbar. The yields of simple hydrocarbons in these experiments and an estimate of precipitating electron flux consistent with the Voyager ultraviolet spectroscopy results indicate the globally averaged auroral processing rate of CH4 to higher hydrocarbons approximately equal to 3 x 10(6) C cm-2 s-1, comparable to the globally averaged photochemical production rate. The local rate approximately 2 x 10(8) C cm-2 s-1 in the auroral zones (approximately 20 degrees in diameter) at 15 degrees S and 45 degrees N latitude greatly exceeds the photochemical rate. Even at very low XCH4 approximately equal to 10(-3) the yield (summed over all products) G > approximately 10(-2) C/100 eV and the average slope alpha = > approximately -0.4, where the summation is over all product molecules of a given carbon number eta and the square brackets denote abundance. The yield therefore decreases slowly with molecular complexity: hydrocarbons through C7Hx should be present in auroral zones at abundances > approximately 10(-2) of the simplest C2 hydrocarbons. Saturated hydrocarbons (C2H6, C3H8, C4H10, etc.) are mostly shielded from photodissociation by C2H2 and will therefore persist at the sunlit, as well as the currently dark, magnetic polar regions.

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.

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.

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 (approximately equal to 1.65) and k (approximately equal to 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 (lambda), including the 4.6 micrometers 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.

Titan: a laboratory for prebiological organic chemistry.

When we examine the atmospheres of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune), the satellites in the outer solar system, comets, and even--through microwave and infrared spectroscopy--the cold dilute gas and grains between the stars, we find a rich organic chemistry, presumably abiological, not only in most of the solar system but throughout the Milky Way galaxy. In part because the composition and surface pressure of the Earth's atmosphere 4 x 10(9) years ago are unknown, laboratory experiments on prebiological organic chemistry are at best suggestive; but we can test our understanding by looking more closely at the observed extraterrestrial organic chemistry. The present Account is restricted to atmospheric organic chemistry, primarily on the large moon of Saturn. Titan is a test of our understanding of the organic chemistry of planetary atmospheres. Its atmospheric bulk composition (N2/CH4) is intermediate between the highly reducing (H2/He/CH4/NH3/H2O) atmospheres of the Jovian planets and the more oxidized (N2/CO2/H2O) atmospheres of the terrestrial planets Mars and Venus. It has long been recognized that Titan's organic chemistry may have some relevance to the events that led to the origin of life on Earth. But with Titan surface temperatures approximately equal to 94 K and pressures approximately equal to 1.6 bar, the oceans of the early Earth have no ready analogue on Titan. Nevertheless, tectonic events in the water ice-rich interior or impact melting and slow re-freezing may lead to an episodic availability of liquid water. Indeed, the latter process is the equivalent of a approximately 10(3)-year-duration shallow aqueous sea over the entire surface of Titan.

CH4/NH3/H2O spark tholin: chemical analysis and interaction with Jovian aqueous clouds.

The organic solid (tholin) produced by spark discharge in a CH4 + NH3 + H2O atmosphere is investigated, along with the separable components of its water-soluble fraction. The chemistry of this material serves as a provisional model for the interaction of Jovian organic heteropolymers with the deep aqueous clouds of Jupiter. Intact (unhydrolyzed) tholin is resolved into four chemically distinct fractions by high-pressure liquid chromatography (HPLC). Gel filtration chromatography reveals abundant components at molecular weights approximately or equal to 600-700 and 200-300 Da. Gas chromatography/mass spectrometry of derivatized hydrolysis products of unfractionated tholin shows about 10% by mass protein and nonprotein amino acids, chiefly glycine, alanine, aspartic acid, beta-alanine, and beta-aminobutyric acid, and 12% by mass other organic acids and hydroxy acids. The stereospecificity of alanine is investigated and shown to be racemic. The four principal HPLC fractions yield distinctly different proportions of amino acids. Chemical tests show that small peptides or organic molecules containing multiple amino acid precursors are a possibility in the intact tholins, but substantial quantities of large peptides are not indicated. Candidate 700-Da molecules have a central unsaturated, hydrocarbon- and nitrile-rich core, linked by acid-labile (ester or amide) bonds to amino acid and carboxylic acid side groups. The core is probably not HCN "polymer." The concentration of amino acids from tholin hydrolysis in the lower aqueous clouds of Jupiter, about 0.1 micromole, is enough to maintain small populations of terrestrial microorganisms even if the amino acids must serve as the sole carbon source.

Plasma discharge in N2 + CH4 at low pressures: experimental results and applications to Titan.

We report the yields of gaseous hydrocarbons and nitriles produced in a continuous flow, low-dose, cold plasma discharge excited in a 10% CH4, 90% N2 atmosphere at 295 K and pressures p of 17 and 0.24 mbar, and use the results to compute expected abundances of minor constituents in Titan's atmosphere. These experiments are, by design, relevant to the atmospheric chemistry induced by cosmic rays in Titan's troposphere and (at the lower pressure) to chemistry initiated by Saturnian magnetospheric electrons and other charged particle sources which excite stratospheric aurorae. At p = 17 mbar, 59 gaseous species including 27 nitriles are detected in overall yield 4.0 (C + N) atoms incorporated into products per 100 eV (heV). At p = 0.24 mbar, 19 species are detected, including six nitriles and three other unidentified N-bearing compounds; the yield is 0.79 (C + N)/heV, a mild decrease with pressure. The types of molecules formed change more markedly, with high degrees of multiple bonding at 0.24 mbar prevailing over more H-saturated molecules at 17 mbar. The molecules and yields at 0.24 mbar bear a striking resemblance to the minor constituents found in Titan's atmosphere, all of which are abundant products in the laboratory experiment. Using the altitude-integrated flux of charged particle energy deposition at Titan, the laboratory yields at p = 0.24 mb, and a simple eddy mixing model, we compute absolute stratospheric column abundances and mole fractions. These are found to be in very good agreement with the Voyager IRIS observations. Except for the primarily photochemical products, C2H6 and C3H8, the match is much better than that obtained by photochemical-kinetic models, demonstrating that properly designed laboratory experiments are directly applicable to modeling radiation-chemical processes in planetary atmospheres. On the basis of this agreement we expect CH3-C triple bond N (ethanenitrile = acetonitrile) CH2=CH-CH=CH2 (1,3-butadiene), CH2=C=CH2 (1,2-propadiene = allene), and CH2=CH-C triple bond CH (1-buten-3-yne) to be present at mol fractions X > 10(-9), and CH2=CH-C triple bond N (propenenitrile), CH3-CH=CH2 (propene), and CH3-CH2-C triple bond N (propanenitrile) at X > 10(-10) in Titan's atmosphere.

Chemical investigation of Titan and Triton tholins.

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C > 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molecules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Optical properties of Erwinia herbicola bacteria at 0.190-2.50 microm.

We measure the complex index of refraction of Erwina herbicola (also known as Enterobacter agglomerans or Pantoea agglomerans) bacteria (ATTC 33243) over the spectral region from 0.190 to 2.50 microm (4000-52,632 cm(-1)). Transmission measurements are made on solid films of E. herbicola and on suspensions of the bacteria in water. These measurements, combined with spectral reflectance and Kramers-Krönig analysis, allow the determination of the real and imaginary parts over the entire wavelength interval. Accurate and consistent results are obtained for this complex and difficult to measure material. This is part of a continuing series of measurements of the optical constants of representative biological materials that are applicable to the development of methods for detection of airborne biological contaminants, where the material under study is used as a surrogate for a pathogenic agent.

Optical properties of ovalbumin in 0.130-2.50 microm spectral region.

In our continuing series of measurements of the complex index of refraction for representative samples of biological materials, we measured ovalbumin (egg albumin) over the spectral region from 0.130 (76,923 cm(-1)) to 2.50 microm (4000 cm(-1)). Films of ovalbumin suitable for optical analyses were prepared and measured in addition to solutions of ovalbumin in water. We show several examples of how the methods used in this study produced accurate results for this complex and difficult to measure material. The present work is applicable to quantitative optical studies involving ovalbumin and other serpin proteins, as well as the study of proteinaceous toxins.

Solid organic residues produced by irradiation of hydrocarbon-containing H2O and H2O/NH3 ices: infrared spectroscopy and astronomical implications.

Methane clathrate (CH4 nH2O)--expected in cometary nuclei, in outer Solar System satellites, and perhaps in interstellar grains--as well as ices prepared from other combinations of CH4, C2H6, or C2H2 with H2O (and sometimes with NH3) were irradiated at 77 degrees K by plasma discharge. CH4 clathrate and other H2O/hydrocarbon ices color and darken noticeably after a dose approximately 10(8) to approximately 10(9) erg cm-2 over a period of 1-10 hr. Upon evaporation of the now yellowish to tan irradiated ices, a colored solid film adheres to the walls of the reaction vessel at room temperature. Transmission measurements of these organic films were made from 2.5 to 50 micrometers wavelength. The residue left after CH4 nH2O irradiation exhibits IR bands which we tabulate and identify with alkane, aldehyde, alcohol, and perhaps alkene and substituted aromatic functional groups. Aldehydes are especially well indicated, and may be related to recent claims of polyoxymethylene (H2CO)n in the coma of Comet Halley. Spectra presented here are compared with previous studies of UV or proton-irradiated, nonenclathrated hydrocarbon-containing ices may be useful for interpreting infrared features found in the spectra of comets and interstellar grains.

Microbial metabolism of tholin.

In this paper, we show that a wide variety of common soil bacteria are able to obtain their carbon and energy needs from tholin (a class of complex organic heteropolymers thought to be widely distributed through the solar system; in this case tholin was produced by passage of electrical discharge through a mixture of methane, ammonia, and water vapor). We have isolated aerobic, anaerobic, and facultatively anaerobic bacteria which are able to use tholin as a sole carbon source. Organisms which metabolize tholin represent a variety of bacterial genera including Clostridium, Pseudomonas, Bacillus, Acinetobacter, Paracoccus, Alcaligenes, Micrococcus, Corynebacterium, Aerobacter, Arthrobacter, Flavobacterium, and Actinomyces. Aerobic tholin-using bacteria were first isolated from soils containing unusual or sparse carbon sources. Some of these organisms were found to be facultatively anaerobic. Strictly anaerobic tholin-using bacteria were isolated from both carbon-rich and carbon-poor anaerobic lake muds. In addition, both aerobic and anaerobic tholin-using bacteria were isolated from common soil collected outside the laboratory building. Some, but not all, of the strains that were able to obtain carbon from tholin were also able to obtain their nitrogen requirements from tholin. Bacteria isolated from common soils were tested for their ability to obtain carbon from the water-soluble fraction, the ethanol-soluble fraction, and the water/ethanol-insoluble fraction of the tholin. Of the 3.5 x 10(7) bacteria isolated per gram of common soils, 1.7, 0.5, and 0.2%, respectively, were able to obtain their carbon requirements from the water-soluble fraction, the ethanol-soluble fraction and the water/ethanol-insoluble fraction of the tholin. The palatability of tholins to modern microbes may have implications for the early evolution of microbial life on Earth. Tholins may have formed the base of the food chain for an early heterotrophic biosphere before the evolution of autotrophy on the early Earth. Where tholins are present on other planets, they could possibly be metabolized by contaminant microorganisms transported to these bodies via spacecraft. Thus, the presence of tholins should be taken into account when evaluating the planetary quarantine requirements for probes to other planets.

Optical properties of poly-HCN and their astronomical applications.

Matthews (1992) has proposed that HCN "polymer" is ubiquitous in the solar system. We apply vacuum deposition and spectroscopic techniques previously used on synthetic organic heteropolymers (tholins), kerogens, and meteoritic organic residues to the measurement of the optical constants of poly-HCN in the wavelength range 0.05-40 micrometers. These measurements allow quantitative comparison with spectrophotometry of organic-rich bodies in the outer solar system. In a specific test of Matthews' hypothesis, poly-HCN fails to match the optical constants of the haze of the Saturnian moon, Titan, in the visible and near-infrared derived from astronomical observations and standard models of the Titan atmosphere. In contrast, a tholin produced from a simulated Titan atmosphere matches within the probable errors. Poly-HCN is much more N-rich than Titan tholin.

Amino acids derived from Titan tholins.

An organic heteropolymer (Titan tholin) was produced by continuous dc discharge through a 0.9 N2/0.1 CH4 gas mixture at 0.2 mbar pressure, roughly simulating the cloudtop atmosphere of Titan. Treatment of this tholin with 6N HCl yielded 16 amino acids by gas chromatography after derivatization of N-trifluroacetyl isopropyl esters on two different capillary columns. Identifications were confirmed by GC/MS. Glycine, aspartic acid, and alpha- and beta-alanine were produced in greatest abundance; the total yield of amino acids was approximately 10(-2), approximately equal to the yield of urea. The presence of "nonbiological" amino acids, the absence of serine, and the fact that the amino acids are racemic within experimental error together indicate that these molecules are not due to microbial or other contamination, but are derived from the tholin. In addition to the HCN, HC2CN, and (CN)2 found by Voyager, nitriles and aminonitriles should be sought in the Titanian atmosphere and, eventually, amino acids on the surface. These results suggest that episodes of liquid water in the past or future of Titan might lead to major further steps in prebiological organic chemistry on that body.