Gas/solid carbon branching ratios in surface-mediated reactions and the incorporation of carbonaceous material into planetesimals.

We report the ratio of the initial carbon available as CO that forms gas-phase compounds compared to the fraction that deposits as a carbonaceous solid (the gas/solid branching ratio) as a function of time and temperature for iron, magnetite, and amorphous iron silicate smoke catalysts during surface-mediated reactions in an excess of hydrogen and in the presence of N2. This fraction varies from more than 99% for an amorphous iron silicate smoke at 673 K to less than 40% for a magnetite catalyst at 873 K. The CO not converted into solids primarily forms methane, ethane, water, and CO2, as well as a very wide range of organic molecules at very low concentration. Carbon deposits do not form continuous coatings on the catalytic surfaces, but instead form extremely high surface area per unit volume "filamentous" structures. While these structures will likely form more slowly but over much longer times in protostellar nebulae than in our experiments due to the much lower partial pressure of CO, such fluffy coatings on the surfaces of chondrules or calcium aluminum inclusions could promote grain-grain sticking during low-velocity collisions.

Measuring the optical properties of astrophysical dust analogues: instrumentation and methods.

Dust is found throughout the universe and plays an important role for a wide range of astrophysical phenomena. In recent years, new IR facilities have provided powerful new data for understanding these phenomena. However, interpretation of these data is often complicated by a lack of complementary information about the optical properties of astronomically relevant materials. The Optical Properties of Astronomical Silicates with Infrared Techniques (OPASI-T) program at NASA's Goddard Space Flight Center is designed to provide new high-quality laboratory data from which we can derive the optical properties of astrophysical dust analogues. This program makes use of multiple instruments, including new equipment designed and built specifically for this purpose. The suite of instruments allows us to derive optical properties over a wide wavelength range, from the near-IR through the millimeter, also providing the capability for exploring how these properties depend upon the temperature of the sample. In this paper, we discuss the overall structure of the research program, describe the new instruments that have been developed to meet the science goals, and demonstrate the efficacy of these tools.

The influence of buoyant convection on the nucleation of n-propanol in thermal diffusion cloud chambers.

A two-dimensional numerical model has been applied to three thermal diffusion cloud chamber (TDCC) investigations of n-propanol in helium taken by two different research groups to provide a quantitative example of how the results in these chambers can be affected by buoyant convection. In the first set of TDCC data, corrections for buoyancy resolve an apparent discontinuity in critical supersaturation data and also yield nucleation rate data that tend to agree better with higher rate, expansion-based studies at the same temperature. In the second TDCC study, the nucleation of propanol was studied over an extended pressure range. When the model was applied to these data, the possible variation in supersaturation values due to convection induced by conditions at the chamber sidewall was found to be comparable in magnitude to the experimentally observed range and may be responsible for some of this observed pressure dependence. In the third TDCC study, the combination of an error in a transport property and buoyant convection appear responsible for a perceived pressure effect in the experimental data. After correcting for this transport property and for buoyancy, the results at higher temperatures agree quite closely with the predictions of classical nucleation theory.

Did a Complex Carbon Cycle Operate in the Inner Solar System?

Solids in the interstellar medium consist of an intimate mixture of silicate and carbonaceous grains. Because 99% of silicates in meteorites were reprocessed at high temperatures in the inner regions of the Solar Nebula, we propose that similar levels of heating of carbonaceous materials in the oxygen-rich Solar Nebula would have converted nearly all carbon in dust and grain coatings to CO. We discuss catalytic experiments on a variety of grain surfaces that not only produce gas phase species such as CH4, C2H6, C6H6, C6H5OH, or CH3CN, but also produce carbonaceous solids and fibers that would be much more readily incorporated into growing planetesimals. CH4 and other more volatile products of these surface-mediated reactions were likely transported outwards along with chondrule fragments and small Calcium Aluminum-rich Inclusions (CAIs) to enhance the organic content in the outer regions of the nebula where comets formed. Carbonaceous fibers formed on the surfaces of refractory oxides may have significantly improved the aggregation efficiency of chondrules and CAIs. Carbonaceous fibers incorporated into chondritic parent bodies might have served as the carbon source for the generation of more complex organic species during thermal or hydrous metamorphic processes on the evolving asteroid.

DEFENDING THE EARTH FROM LONG-PERIOD COMETS AND SNEAKY ASTEROIDS: SHORT TERM THREAT RESPONSE REQUIRES LONG TERM PREPARATION.

Comets, such as the recent Comet C/2013 A1 (Siding Spring) can impact terrestrial planets with very short warning times: for Siding Spring the time from discovery to closest approach to Mars (135,000 km) was less than 22 months. Short warning times are also possible for certain asteroids approaching on unfavorable orbits, e.g., from the direction of the Sun. The time required to design, build, test and launch a high-reliability Interceptor spacecraft is on the order of 5 years, a timescale incompatible with threat mitigation for such short warning times. A potential solution is to build the interceptor before the threat is detected and put it into storage until it is required. Launch of a stored spacecraft could be accomplished in much less than a year after authorization based on experience with the DSCOVR (Deep Space Climate Observatory) program managed by NASA's Goddard Space Flight Center. While asteroidal impacts are of order 100 times more likely than cometary impacts, comet impacts can carry more than 100 times the energy of a typical asteroid threat, making their destructive power nearly equal. Cometary threats have been largely ignored to date, a situation that needs to change as our Planetary Defense efforts become more mature. An idealized threat response system will be described.

On the Use of Fourier Transform Infrared (FT-IR) Spectroscopy and Synthetic Calibration Spectra to Quantify Gas Concentrations in a Fischer-Tropsch Catalyst System.

One possible origin of prebiotic organic material is that these compounds were formed via Fischer-Tropsch-type (FTT) reactions of carbon monoxide and hydrogen on silicate and oxide grains in the warm, inner-solar nebula. To investigate this possibility, an experimental system has been built in which the catalytic efficiency of different grain-analog materials can be tested. During such runs, the gas phase above these grain analogs is sampled using Fourier transform infrared (FT-IR) spectroscopy. To provide quantitative estimates of the concentration of these gases, a technique in which high-resolution spectra of the gases are calculated using the High-Resolution Transmission Molecular Absorption (HITRAN) database is used. Next, these spectra are processed via a method that mimics the processes giving rise to the instrumental line shape of the FT-IR spectrometer, including apodization, self-apodization, and broadening due to the finite resolution. The result is a very close match between the measured and computed spectra. This technique was tested using four major gases found in the FTT reactions: carbon monoxide, methane, carbon dioxide, and water. For the ranges typical of the FTT reactions, the carbon monoxide results were found to be accurate to within 5% and the remaining gases accurate to within 10%. These spectra can then be used to generate synthetic calibration data, allowing the rapid computation of the gas concentrations in the FTT experiments.

The catalytic potential of cosmic dust: implications for prebiotic chemistry in the solar nebula and other protoplanetary systems.

The synthesis of important prebiotic molecules is fundamentally reliant on basic starting ingredients: water, organic species [e.g., methane (CH(4))], and reduced nitrogen compounds [e.g., ammonia (NH(3)), methyl cyanide (CH(3)CN) etc.]. However, modern studies conclude that the primordial Earth's atmosphere was too rich in CO, CO(2), and water to permit efficient synthesis of such reduced molecules as envisioned by the classic Miller-Urey experiment. Other proposed sources of terrestrial nitrogen reduction, like those within submarine vent systems, also seem to be inadequate sources of chemically reduced C-H-O-N compounds. Here, we demonstrate that nebular dust analogs have impressive catalytic properties for synthesizing prebiotic molecules. Using a catalyst analogous to nebular iron silicate condensate, at temperatures ranging from 500K to 900K, we catalyzed both the Fischer-Tropsch conversion of CO and H(2) to methane and water, and the corresponding Haber-Bosch synthesis of ammonia from N(2) and H(2). Remarkably, when CO, N(2), and H(2) were allowed to react simultaneously, these syntheses also yielded nitrogen-containing organics such as methyl amine (CH(3)NH(2)), acetonitrile (CH(3)CN), and N-methyl methylene imine (H(3)CNCH(2)). A fundamental consequence of this work for astrobiology is the potential for a natural chemical pathway to produce complex chemical building blocks of life throughout our own Solar System and beyond.

The NASA Astrobiology Roadmap.

The NASA Astrobiology Roadmap provides guidance for research and technology development across the NASA enterprises that encompass the space, Earth, and biological sciences. The ongoing development of astrobiology roadmaps embodies the contributions of diverse scientists and technologists from government, universities, and private institutions. The Roadmap addresses three basic questions: how does life begin and evolve, does life exist elsewhere in the universe, and what is the future of life on Earth and beyond? Seven Science Goals outline the following key domains of investigation: understanding the nature and distribution of habitable environments in the universe, exploring for habitable environments and life in our own Solar System, understanding the emergence of life, determining how early life on Earth interacted and evolved with its changing environment, understanding the evolutionary mechanisms and environmental limits of life, determining the principles that will shape life in the future, and recognizing signatures of life on other worlds and on early Earth. For each of these goals, Science Objectives outline more specific high priority efforts for the next three to five years. These eighteen objectives are being integrated with NASA strategic planning.

Experimental studies of the vapor phase nucleation of refractory compounds. VI. The condensation of sodium.

In this paper we discuss the condensation of sodium vapor and the formation of a sodium aerosol as it occurs in a gas evaporation condensation chamber. A one-dimensional model describing the vapor transport to the vapor/aerosol interface was employed to determine the onset supersaturation, in which we assume the observed location of the interface is coincident with a nucleation rate maximum. We then present and discuss the resulting nucleation onset supersaturation data within the context of nucleation theory based on the liquid droplet model. Nucleation results appear to be consistent with a cesium vapor-to-liquid nucleation study performed in a thermal diffusion cloud chamber.