Gene D. McDonald

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.

A search for endogenous amino acids in the Martian meteorite EETA79001.

The Antarctic shergottite EETA79001 is believed to be an impact-ejected fragment of the planet Mars. Samples of the carbonate (white druse) and the basaltic (lithology A) components from this meteorite have been found to contain amino acids at a level of approximately 1 ppm and 0.4 ppm, respectively. The detected amino acids consist almost exclusively of the L-enantiomers of the amino acids commonly found in proteins, and are thus terrestrial contaminants. There is no indication of the presence of alpha-aminoisobutyric acid, one of the most abundant amino acids in several carbonaceous chondrites. The relative abundances of amino acids in the druse material resemble those in Antarctic ice, suggesting that the source of the amino acids may be ice meltwater. The level of amino acids in EETA79001 druse is not by itself sufficient to account for the 600-700 ppm of volatile C reported in druse samples and suggested to be from endogenous martian organic material. However, estimates of total terrestrial organic C present in the druse material based on our amino acid analyses and the organic C content of polar ice can account for most of the reported putative organic C in EETA79001 druse.

Biochemical Constraints in a Protobiotic Earth Devoid of Basic Amino Acids: The “BAA(-) World”

It has been hypothesized in this journal and elsewhere, based on surveys of published data from prebiotic synthesis experiments and carbonaceous meteorite analyses, that basic amino acids such as lysine and arginine were not abundant on prebiotic Earth. If the basic amino acids were incorporated only rarely into the first peptides formed in that environment, it is important to understand what protobiotic chemistry is possible in their absence. As an initial test of the hypothesis that basic amino acid negative [BAA(-)] proteins could have performed at least a subset of protobiotic chemistry, the current work reports on a survey of 13 archaeal and 13 bacterial genomes that has identified 61 modern gene sequences coding for known or putative proteins not containing arginine or lysine. Eleven of the sequences found code for proteins whose functions are well known and important in the biochemistry of modern microbial life: lysine biosynthesis protein LysW, arginine cluster proteins, copper ion binding proteins, bacterial flagellar proteins, and PE or PPE family proteins. These data indicate that the lack of basic amino acids does not prevent peptides or proteins from serving useful structural and biochemical functions. However, as would be predicted from fundamental physicochemical principles, we see no fossil evidence of prebiotic BAA(-) peptide sequences capable of interacting directly with nucleic acids.

Radiation Chemistry in the Jovian Stratosphere: Laboratory Simulations

Low-pressure continuous-flow laboratory simulations of plasma induced chemistry in H2/He/CH4/NH3 atmospheres show radiation yields of hydrocarbons and nitrogen-containing organic compounds that increase with decreasing pressure in the range 2-200 mbar. Major products of these experiments that have been observed in the Jovian atmosphere are acetylene (C2H2), ethylene (C2H4), ethane (C2H6), hydrogen cyanide (HCN), propane (C3H8), and propyne (C3H4). Major products that have not yet been observed on Jupiter include acetonitrile (CH3CN), methylamine (CH3NH2), propene (C3H6), butane (C4H10), and butene (C4H8). Various other saturated and unsaturated hydrocarbons, as well as other amines and nitriles, are present in these experiments as minor products. We place upper limits of 10(6)-10(9) molecules cm-2 sec-1 on production rates of the major species from auroral chemistry in the Jovian stratosphere, and calculate stratospheric mole fraction contributions. This work shows that auroral processes may account for 10-100% of the total abundances of most observed organic species in the polar regions. Our experiments are consistent with models of Jovian polar stratospheric aerosol haze formation from polymerization of acetylene by secondary ultraviolet processing.

Evidence from scanning electron microscopy ofexperimental influences on the morphology of Triton andTitan tholins

Abstract To simulate experimentally the production of aerosols in the atmospheres of Titan andTriton, we have studied organic material (tholins) obtained by inductively coupled plasma fromCH4 : N2 gas mixtures, with ratios 10 : 90 for Titan simulations and 0.1 : 99.9 for Tritonsimulations. Observation of tholins by high performance scanning electron microscopy showsthat tholin morphology varies with the chemical composition of the initial gas mixture. Althoughthe role of the experimental design (especially the diameter of the discharge chamber) and theflux of matter were not fully investigated, it appears that they have a significant effect not on theoverall morphology of the tholins but on the size distribution of the particles.

For which compounds do we search in extraterrestrial samples for evidence of abiotic and/or biotic chemistry?

Any strategy for investigating whether abiotic and/or biotic organic molecules are present on planetary bodies in the solar system should focus on compounds which are readily synthesized under plausible prebiotic conditions, play an essential role in biochemistry as we know it and have properties such as chirality (handedness) which can be used to distinguish between abiotic vs. biotic origins. Amino acids are one of the few compound classes that fulfill all these requirements. They are synthesized in high yields in prebiotic simulation experiments, are one of the more abundant types of organic compounds present in carbonaceous meteorites and only the L-enantiomers are used in the proteins and enzymes in life on Earth. In contrast, polycylic aromatic hydrocarbons which have recently been detected in some Martian meteorites, have no role in biochemistry on Earth, and their molecular architecture, with the possible exception of the stable isotope composition, cannot be used to determine whether they were produced by biotic or abiotic processes. Recent results indicate that amino acids and their amine decomposition products can be directly isolated from samples using sublimation (450 degree(s) to 750 degree(s)C) under partial vacuum, thus eliminating the use of the aqueous reagents commonly used in the laboratory-based isolation of amino acids. A relatively new technology which shows promise for spacecraft-based amino acid analysis is microchip-based capillary electrophoresis. The actual separation hardware, including buffer reservoirs and derivatization reaction chambers, can be etched onto glass microchips with dimensions on the order of cm. This methodology offers the best potential for a compact, rugged, low-mass instrument package for in situ amino acid analyses during future space missions to Mars, Europa and comets.