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Cosmic dust analog simulation in a microgravity environment: the STARDUST program.

We have undertaken a project called STARDUST which is a collaboration with Italian and American investigators. The goals of this program are to study the condensation and coagulation of refractory materials from the vapor and to study the properties of the resulting grains as analogs to cosmic dust particles. To reduce thermal convective currents and to develop valuable experience in designing an experiment for the Gas-Grain Simulation Facility aboard Space Station Freedom we have built and flown a new chamber to study these processes under periods of microgravity available on NASA's KC-135 Research Aircraft. Preliminary results from flights with magnesium and zinc are discussed.

Cosmic Dust↗

Learning to tell Neoproterozoic time.

In 1989, the International Commission on Stratigraphy established a Working Group on the Terminal Proterozoic Period. Nine years of intensive, multidisciplinary research by scientists from some two dozen countries have markedly improved the framework for the correlation and calibration of latest Proterozoic events. Three principal phenomena--the Marinoan ice age, Ediacaran animal diversification, and the beginning of the Cambrian Period--specify the limits and character of this interval, but chemostratigraphy and biostratigraphy based on single-celled microfossils (acritarchs), integrated with high-resolution radiometric dates, provide the temporal framework necessary to order and evaluate terminal Proterozoic tectonic, biogeochemical, climatic, and biological events. These data also provide a rational basis for choosing the Global Stratotype Section and Point (GSSP) that will define the beginning of this period. A comparable level of stratigraphic resolution may be achievable for the preceding Cryogenian Period, providing an opportunity to define this interval, as well, in chronostratigraphic terms--perhaps bounded at beginning and end by the onset of Sturtian glaciation and the decay of Marinoan ice sheets, respectively. Limited paleontological, isotopic, and radiometric data additionally suggest a real but more distant prospect of lower Neoproterozoic correlation and stratigraphic subdivision.

Animals↗

Astrobiology, the transcendent science: the promise of astrobiology as an integrative approach for science and engineering education and research.

Astrobiology is rapidly gaining the worldwide attention of scientists, engineers and the public. Astrobiology's captivation is due to its inherently interesting focus on life, its origins and distribution in the Universe. Because of its remarkable breadth as a scientific field, astrobiology touches on virtually all disciplines in the physical, biological and social sciences as well as engineering. The multidisciplinary nature and the appeal of its subject matter make astrobiology ideal for integrating the teaching of science at all levels in educational curricula. The rationale for implementing novel educational programs in astrobiology is presented along with specific research and educational policy recommendations.

Biological Evolution↗

Concepts and approaches to in situ luminescence dating of Martian sediments.

In this paper we present the concept of a robotic instrument for in situ luminescence dating of near-surface sediments on Mars. The scientific objectives and advantages to be gained from the development of such an instrument are described, and the challenges presented by the Mars surface environment to the design and operation of the instrument are outlined.

Cosmic Radiation↗

Sources and sinks for ammonia and nitrite on the early Earth and the reaction of nitrite with ammonia.

An analysis of sources and sinks for ammonia and nitrite on the early Earth was conducted. Rates of formation and destruction, and steady state concentrations of both species were determined by steady state kinetics. The importance of the reaction of nitrite with ammonia on the feasibility of ammonia formation from nitrite was evaluated. The analysis considered conditions such as temperature, ferrous iron concentration, and pH. For sinks we considered the reduction of nitrite to ammonia, reaction between nitrite and ammonia, photochemical destruction of both species, and destruction at hydrothermal vents. Under most environmental conditions, the primary sink for nitrite is reduction to ammonia. The reaction between ammonia and nitrite is not an important sink for either nitrite or ammonia. Destruction at hydrothermal vents is important at acidic pH's and at low ferrous iron concentrations. Photochemical destruction, even in a worst case scenario, is unimportant under many conditions except possibly under acidic, low iron concentration, or low temperature conditions. The primary sink for ammonia is photochemical destruction in the atmosphere. Under acidic conditions, more of the ammonia is tied up as ammonium (reducing its vapor pressure and keeping it in solution) and hydrothermal destruction becomes more important.

Ammonia↗

On the prebiotic role of iron and sulfur.

Thermodynamic data (Sillen, L. G.: 1966, Arkiv Kemi, 25, 159) indicate that there is little support for the idea that metabolic sulfur cycles were involved in prebiotic and early life processes, since under reducing conditions the 'equilibrium' concentration of sulfur in the primordial seas should have been very low, < 10(-8) M. However, it is suggested that metabolic sulfur cycles may have become important when oxygen evolved, when iron(II) ions disappeared from the seas, and when large amounts of sulfur were released from their iron sulfide sources.

Earth, Planet↗

Photosynthesis and the origin of life.

The origin and evolution of photosynthesis is considered to be the key to the origin of life. This eliminates the need for a soup as the synthesis of the bioorganics are to come from the fixation of carbon dioxide and nitrogen. No soup then no RNA world or Protein world. Cyanobacteria have been formed by the horizontal transfer of green sulfur bacterial photoreaction center genes by means of a plasmid into a purple photosynthetic bacterium. The fixation of carbon dioxide is considered to have evolved from a reductive dicarboxylic acid cycle (Chloroflexus) which was then followed by a reductive tricarboxylic acid cycle (Chlorobium) and finally by the reductive pentose phosphate cycle (Calvin cycle). The origin of life is considered to have occurred in a hot spring on the outgassing early earth. The first organisms were self-replicating iron-rich clays which fixed carbon dioxide into oxalic and other dicarboxylic acids. This system of replicating clays and their metabolic phenotype then evolved into the sulfide rich region of the hotspring acquiring the ability to fix nitrogen. Finally phosphate was incorporated into the evolving system which allowed the synthesis of nucleotides and phospholipids. If biosynthesis recapitulates biopoesis, then the synthesis of amino acids preceded the synthesis of the purine and pyrimidine bases. Furthermore the polymerization of the amino acid thioesters into polypeptides preceded the directed polymerization of amino acid esters by polynucleotides. Thus the origin and evolution of the genetic code is a late development and records the takeover of the clay by RNA.

Aluminum Silicates↗

Amino acid formation in gas mixtures by high energy particle irradiation.

Amino acids were formed from carbon monoxide, nitrogen and water, which are possible constituents of the primitive earth's atmosphere, by irradiation with high energy particles (components of cosmic rays). Glycine yield was proportional to the total energy deposited to the gas mixture, and its G-value was as high as 0.02 when the carbon monoxide/nitrogen ratio was 1. Based on an estimate of the effective energies of various types of energy sources available in the primitive earth's atmosphere for amino acid synthesis, it is suggested that cosmic rays were one of the most important energy sources for the synthesis of amino acids on the primitive earth.

Amino Acids↗

Experimental shock chemistry of aqueous amino acid solutions and the cometary delivery of prebiotic compounds.

A series of shock experiments were conducted to assess the feasibility of the delivery of organic compounds to the Earth via cometary impacts. Aqueous solutions containing near-saturation levels of amino acids (lysine, norvaline, aminobutyric acid, proline, and phenylalanine) were sealed inside stainless steel capsules and shocked by ballistic impact with a steel projectile plate accelerated along a 12-m-long gun barrel to velocities of 0.5-1.9 km sec-1. Pressure-temperature-time histories of the shocked fluids were calculated using 1D hydrodynamical simulations. Maximum conditions experienced by the solutions lasted 0.85-2.7 microseconds and ranged from 5.1-21 GPa and 412-870 K. Recovered sample capsules were milled open and liquid was extracted. Samples were analyzed using high performance liquid chromatography (HPLC) and mass spectrometry (MS). In all experiments, a large fraction of the amino acids survived. We observed differences in kinetic behavior and the degree of survivability among the amino acids. Aminobutyric acid appeared to be the least reactive, and phenylalanine appeared to be the most reactive of the amino acids. The impact process resulted in the formation of peptide bonds; new compounds included amino acid dimers and cyclic diketopiperazines. In our experiments, and in certain naturally occurring impacts, pressure has a greater influence than temperature in determining reaction pathways. Our results support the hypothesis that significant concentrations of organic material could survive a natural impact process.

Amino Acids↗

Interstellar ices as a source of CN-bearing molecules in protoplanetary disks.

A reliable model for the composition and evolution of interstellar ices in regions of active star formation is fundamental to our quest to determine the organic inventory of planetesimals in the early Solar System. This has become a realistic goal since the launch of the Infrared Space Observatory, which provides a facility for infrared spectroscopy unhindered by telluric absorption over the entire spectral range of vibrational modes in solids of exobiological interest. Interstellar molecules detected in the solid phase to date include H2O, NH3, CO, CO2, CH3OH, CH4, H2CO, OCS and HCOOH, together with a C identical to N-bonded absorber generically termed 'XCN'. In this article, we focus on cosmic synthesis of CN-bearing species, as this important class of prebiotic molecules may not have formed endogenously in significant quantities on early Earth if conditions were not highly reducing. Experiments in which interstellar ice analogs are subject to UV photolysis or energetic ion bombardment yield CN-rich residues with a spectral signature that matches a corresponding feature observed in young protostars enshrouded in dust and gas. CN-bearing species are also present in cometary ices, with a combined abundance comparable to the lower end of the range observed in protostars. Energetic processing of interstellar ices is thus a viable and potentially significant source of CN compounds in protoplanetary disks.

Evolution, Chemical↗

Contributions of icy planetesimals to the Earth's early atmosphere.

Laboratory experiments on the trapping of gases by ice forming at low temperatures implicate comets as major carriers of the heavy noble gases to the inner planets. These icy planetesimals may also have brought the nitrogen compounds that ultimately produced atmospheric N2. However, if the sample of three comets analyzed so far is typical, the Earth's oceans cannot have been produced by comets alone, they require an additional source of water with low D/H. The highly fractionated neon in the Earth's atmosphere may also indicate the importance of non-icy carriers of volatiles. The most important additional carrier is probably the rocky material comprising the bulk of the mass of these planets. Venus may require a contribution from icy planetesimals formed at the low temperatures characteristic of the Kuiper Belt.

Earth, Planet↗

Exploring for a record of ancient Martian life.

The immediate task facing exopaleontology is to define a strategy to explore Mars for a fossil record during the decade-long exploration program that lies ahead. Consideration of the quality of paleontological information preserved under different geological conditions is important if we are to develop a strategy with broad applicability. The preservation of microbial fossils is strongly influenced by the physical, chemical, and biological factors of the environment which, acting together, determine the types of information that will be captured and retained in the rock record. In detrital sedimentary systems, preservation is favored by rapid burial in fine-grained, clay-rich sediments. In chemical sedimentary systems, preservation is enhanced by rapid entombment in fine-grained chemical precipitates. For long-term preservation, host rocks must be composed of stable minerals that are resistant to chemical weathering and that form an impermeable matrix and closed chemical system to protect biosignatures from alteration during subsequent diagenesis or metamorphism. In this context, host rocks composed of highly ordered, chemically stable mineral phases, like silica (e.g., cherts) or phosphate (e.g., phosphorites), are especially favored. Such lithologies tend to have very long crustal residence times and, along with carbonates and shales, are the most common host rocks for the Precambrian microfossil record on Earth. Although we make the defensible assumption that Mars was more like the Earth early in its history, clearly, the geological and historical differences between the two planets are many. Such differences must be carefully considered when adapting an Earth-based strategy to Mars.

Carbonates↗

Alteration processes in volcanic soils and identification of exobiologically important weathering products on Mars using remote sensing.

Determining the mineralogy of the Martian surface material provides information about the past and present environments on Mars which are an integral aspect of whether or not Mars was suitable for the origin of life. Mineral identification on Mars will most likely be achieved through visible-infrared remote sensing in combination with other analyses on landed missions. Therefore, understanding the visible and infrared spectral properties of terrestrial samples formed via processes similar to those thought to have occurred on Mars is essential to this effort and will facilitate site selection for future exobiology missions to Mars. Visible to infrared reflectance spectra are presented here for the fine-grained fractions of altered tephra/lava from the Haleakala summit basin on Maui, the Tarawera volcanic complex on the northern island of New Zealand, and the Greek Santorini island group. These samples exhibit a range of chemical and mineralogical compositions, where the primary minerals typically include plagioclase, pyroxene, hematite, and magnetite. The kind and abundance of weathering products varied substantially for these three sites due, in part, to the climate and weathering environment. The moist environments at Santorini and Tarawera are more consistent with postulated past environments on Mars, while the dry climate at the top of Haleakala is more consistent with the current Martian environment. Weathering of these tephra is evaluated by assessing changes in the leachable and immobile elements, and through detection of phyllosilicates and iron oxide/oxyhydroxide minerals. Identifying regions on Mars where phyllosilicates and many kinds of iron oxides/oxyhydroxides are present would imply the presence of water during alteration of the surface material. Tephra samples altered in the vicinity of cinder cones and steam vents contain higher abundances of phyllosilicates, iron oxides, and sulfates and may be interesting sites for exobiology.

Evolution, Planetary↗

Water on Mars: isotopic constraints on exchange between the atmosphere and surface.

Using a new measurement of the D/H fractionation efficiency and new estimates of the water loss, we calculate that Mars has the equivalent of a approximately 9 m global water layer in a reservoir that exchanges with the atmosphere. The measured D/H enrichment is about 5 times the terrestrial value, but without exchange, the atmosphere converges on an enrichment of 50 in about 0.5 Ma. Due to the large buffering reservoir and the rapid loss rate (10(-3) pr-micrometers yr-1), the small atmospheric reservoir, averaging 10 pr-micrometers, is unlikely to be in continuous isotopic equilibrium with the full 9 m exchangeable reservoir. Instead, it presumably equilibrates during periods of high obliquity; the atmospheric D/H ratio is expected to be enriched in between such periods. If isotopic exchange with a small (4 mm global layer) reservoir occurs under current conditions, it possible for the atmospheric D/H ratio to be within 10% of its long term equilibrium.

Atmosphere↗

Detection of groundwater conduits in limestones with gravity surveys: data from the area of the Chicxulub Impact crater, Yucatan Peninsula, Mexico.

Small negative gravity anomalies are found in gravity data from along the northwestern shoreline of the Yucatan Peninsula. These anomalies are shown to be due to elongate, shallow anomalous porosity zones in the Tertiary carbonates. These zones are caused primarily by groundwater solution and are presently active conduits for groundwater flow. The association of these small gravity anomalies with known topographic and structural features of the area, which partially overlies the Chicxulub Impact crater, indicates their development was influenced by structures, faults and/or fractures, within the Tertiary and pre-Tertiary carbonates.

Calcium Carbonate↗

A thermodynamic assessment of the potential synthesis of condensed hydrocarbons during cooling and dilution of volcanic gases.

The possibility for abiotic synthesis of condensed hydrocarbons in cooling/diluting terrestrial volcanic gases has been evaluated on the basis of the consideration of metastable chemical equilibria involving gaseous CO, CO2, H2 and H2O. The stabilities of n-alkanes and polycyclic aromatic hydrocarbons (PAHS) have been evaluated for several typical volcanic gas compositions under various conditions for cooling/diluting of quenched volcanic gas. The modeling shows that n-alkanes and PAHs have a thermodynamic potential to form metastably from H2 and CO below approximately 250 degrees C within the stability field of graphite. Despite the predominance of CO2 in volcanic gases, synthesis of hydrocarbons from CO2 and H2 is less favored energetically than from CO and H2. Both low temperature and a high H/C atomic ratio in volcanic gas generally favor stability of hydrocarbons with higher H/C ratios. PAHs are thermodynamically stable at temperatures approximately 10 degrees -50 degrees C higher than large n-alkanes; however, at lower temperatures, PAHs and n-alkanes have similar stabilities and are likely to form metastable mixtures. Both the energetic drive to form hydrocarbons and possible temperatures of formation increase as the oxidation state (fO2) of the volcanic gases decreases and as the cooling/dilution ratios of volcanic gases increase. Synthesis of hydrocarbons is energetically more likely in cooling trapped gases than in ashcloud eruptive columns. Mechanisms for hydrocarbon formation may include Fischer-Tropsch-type synthesis catalyzed by magnetite from solid volcanic products. On the early Earth, Mars, and Jupiter's satellite Europa, several factors would have provided more favorable conditions for hydrocarbon synthesis in volcanic gases than under current terrestrial conditions and might have contributed to the production of organic compounds required for the emergence of life.

Alkanes↗

Greenhouse warming by CH4 in the atmosphere of early Earth.

Earth appears to have been warm during its early history despite the faintness of the young Sun. Greenhouse warming by gaseous CO2 and H2O by itself is in conflict with constraints on atmospheric CO2 levels derived from paleosols for early Earth. Here we explore whether greenhouse warming by methane could have been important. We find that a CH4 mixing ratio of 10(-4) (100 ppmv) or more in Earth's early atmosphere would provide agreement with the paleosol data from 2.8 Ga. Such a CH4 concentration could have been readily maintained by methanogenic bacteria, which are thought to have been an important component of the biota at that time. Elimination of the methane component of the greenhouse by oxidation of the atmosphere at about 2.3-2.4 Ga could have triggered the Earth's first widespread glaciation.

Atmosphere↗

Thickness of tropical ice and photosynthesis on a snowball Earth.

On a completely ice-covered "snowball" Earth the thickness of ice in the tropical regions would be limited by the sunlight penetrating into the ice cover and by the latent heat flux generated by freezing at the ice bottom--the freezing rate would balance the sublimation rate from the top of the ice cover. Heat transfer models of the perennially ice-covered Antarctic dry valley lakes applied to the snowball Earth indicate that the tropical ice cover would have a thickness of 10 m or less with a corresponding transmissivity of > 0.1%. This light level is adequate for photosynthesis and could explain the survival of the eukaryotic algae.

Antarctic Regions↗