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Understanding and controlling water-organic co-transport in amorphous microporous materials

The transport of molecules in microporous material is a significant and active area of research in separation applications. The movement of vapor/liquid molecules in a high-loading condition in microporous spaces is especially challenging to interrogate. This project aims to understand and control the transport of complex water and organic solvent mixtures in varying structures of microporous carbon molecular sieve (CMS) and activated carbon membranes. Modeling of transport behavior in such carbonaceous samples using computational modeling is difficult due to their amorphous structure. Therefore, this research intends to study the transport mechanism of water-organic mixtures by experimentally revealing fundamental transport properties, such as guest sorption amounts as well as diffusion and permeation rates. Considering the different size and guest-host affinity of water and organic solvent molecules, the objective of this research is to understand the structural conditions within the ultramicropores and micropores that generate different types of molecular transport and selection mechanisms within such complex systems. Carbonaceous materials are developed using tailored pyrolysis techniques to pyrolyze polymeric precursors, including polyvinylidene chloride (PVDC),polyvinylidene fluoride (PVDF), polymer of intrinsic microporosity (PIM) -1, and fully aromatic polyamide. The initial stage of the research will focus on the microscopic diffusion and sorption studies of pure component water, xylene isomers, and n,n- dimethylformamide within various carbons. Additional structural investigation on CMS, such as gas physisorption and neutron scattering studies, will be executed to gain deeper insight into these structure-transport relationships. Scanning electron microscopy and X-ray photoelectron microscopy are also used to further characterize these materials. The research will progress to probe mutual diffusion of complex water-organic mixtures within various CMS microstructures. Competitive sorption and permeation studies of the binary mixtures in different microstructural CMS will be followed. The obtained binary mixture transport parameters were used to predict binary water-organic mixtures transport.

36 MATERIALS SCIENCE↗

Time-History Statistics of Soot Formation in A Model Gas Turbine Combustor

Soot formation is a complex dynamic and intermittent process determined by properties of the fuel, combustor design, and combustor operation. Although the major steps in soot formation (i.e., formation of precursors, inception, growth and evolution) are similar for a variety of carbonaceous fuels, applications, and operating conditions, it remains unclear when the temporal transition between these steps occurs. An engineering prediction tool coupled with computational fluid physics (CFD), therefore needs to accurately model all these complex steps. To develop such a model, we propose the time-history concept for understanding the time dependency of soot formation as a function of local properties (i.e., temperature, velocity, local fuel air ratio, etc.). We continue our previous work with modeling the DLR aero-combustor [1] with our updated in-house CFD code, Open National Combustion Code (OpenNCC), that now includes a Multiple Time-Scale Flamelet Progress Variable approach and a the semi-empirical two-equation soot model. We injected massless tracer particles upstream of the injector region of the combustor to collect time-history statistics of the solution variables. The correlations between the collected statistics with respect to the experimental soot volume fraction data showed that time-history effect of certain flow variables, including turbulent kinetic energy (TKE), and multiple species is indeed important for soot formation. We then conducted a time-history based correlation analysis to determine the key species and the concentration ranges critical for soot formation (C6H5-based nucleation, acetylene-based surface growth, and oxidation with OH and O2). Based on the time-history correlation coefficient (THCC) analysis, we propose possible modifications to improve the current two-equation model.

LES↗

Organic Globules with Anomalous Nitrogen Isotopic Compositions in the Tagish Lake Meteorite: Products of Primitive Organic Reactions

Interstellar grains in molecular clouds consist primarily of silicate minerals, organic material, and ices. These interstellar materials are heated and partially evaporated during the birth of the protosolar nebula, and the remaining core-mantle grains grow into large aggregates by collision and subsequent sticking to become planetesimals. The chemical diversity of meteoritic material such as chondrules, Ca-Al rich inclusions and amoeboid-olivine aggregates reflects the material distribution in the late stage of the disk evolution before planetesimal formation began. Organic matter in carbonaceous chondrites should also be considered as a sensitive probe for the extent and timing of high temperature processes in the solar nebula. Current models suggest that many of the organic molecules found in the hydrated carbonaceous chondrite meteorites were synthesized by aqueous processing of a suite of precursor molecules, some of which were interstellar with significant isotopic anomalies, such as excesses of deuterium (D), and 15N.

Nakamura, K.↗

Formation of Cosmic Carbon Dust Analogues in Plasma Reactors

Cosmic carbon dust analogs are produced, processed and analyzed in the laboratory using NASA's COSmIC (COSmIC Simulation Chamber) Facility. These experiments can be used to derive information on the most efficient molecular precursors in the chemical pathways that eventually lead to the formation of carbonaceous grains in the stellar envelopes of carbon stars.

Astrophysics↗

Possible Mechanism(s) in the Photo-Magnetic Production of Enantiomer Excesses.

Among the multitude of organic compounds identified in carbonaceous chondrites are sugar acids ((HO-R)xCOOH), i.e., oxidized counterparts of the common aldehyde sugars (e.g., glyceraldehyde, erythrose, ribose, glucose, etc.). In the historical study of extraterrestrial compounds chiral analyses are particularly significant in origins-of-life studies. Chiral compounds are composed of two non-superposable mirror images or "enantiomers", analogous to a left and right hand. Such molecules are important in contemporary life because biological polymers (proteins, nucleic acids, etc.) are homochiral, i.e., their chiral monomers usually consist of only one of the two enantiomers. It has been shown, at least in one lab setting, that abiotic syntheses of significantly sized RNA polymers do not proceed if the monomers are present in racemic (50:50) amounts. The latter results may argue for, at least, significant enantiomer excesses in organic compounds before the origin of nucleic acids and life. Therefore, the finding that amino acids and sugar acids in carbonaceous chondrites possess enantiomeric excesses may aid in understanding one source of precursors to homochirality. Note: Attachment contains full abstract.

G. Cooper↗

Theoretical studies of chemical reactions related to the formation and growth of polycyclic aromatic hydrocarbons (PAH) and molecular properties of their key intermediates (Final Progress Report)

The formation mechanisms of polycyclic aromatic hydrocarbons, (PAHs) – organic molecules carrying fused benzene rings – are of great interest to scientists and engineers due to their importance in combustion chemistry and astrochemistry. On Earth, PAHs are largely produced in incomplete combustion of fossil fuel and are considered as critical precursors to unwanted soot particles leading to combustion inefficiency and causing air pollution along with detrimental health effects. Simple PAH molecules initially formed in the gas phase, are further involved in a build-up process in combustion flames leading to larger PAH, bowl-shaped nanostructures, fullerenes, and solid-phase species including carbonaceous dust, graphene particles, and soot. In deep space, PAH and their derivatives are potential key intermediates and nucleation sites leading eventually to carbonaceous nanoparticles (“interstellar grains”). Therefore, the understanding of the key processes in the synthesis of PAHs along with their precursors and their degradation mechanisms in combustion systems and in interstellar, circumstellar, and planetary atmospheric environments will provide critical insights into how complex aromatic structures, carbonaceous nanoparticles, and fullerenes are formed and destroyed. Achieving this understanding is an important step in the development of the efficient combustion processes and of the ecofriendly devices with reduced environmental pollution as well as technological strategies for the production of hydrogen and solid carbon through thermal or plasma-assisted pyrolysis of natural gas and biomass. Also, the understanding of the key processes of PAH and soot growth will help in our comprehension of chemical evolution in the universe. Detailed information on the mechanisms and reliable rate constants of the key elementary chemical reactions involved in PAH formation and destruction processes and in inception of soot particles is often missing, with the main deficiencies being the absence of temperature- and pressure-dependent rate constants for the broad range of conditions occurring in various terrestrial and interstellar processes and the lack of data on the reaction products and their branching ratios. Complementary to experimental studies, these gaps in knowledge can be filled by using quantum chemical calculations of reaction potential energy surfaces providing us with accurate energies of reaction products, intermediates, and transition states, revealing the reaction mechanism, and giving the molecular properties required to compute rate constants for relevant reaction steps and product branching ratios using the RRKM-Master Equation (ME) method. Molecular dynamics (MD) simulations can be used in cases when a reaction rate cannot be properly described by statistical theories. During the terminal renewal project period we employed these ab initio/RRKM-ME and MD approaches to complete our studies on several key reactions relevant to the formation/growth of PAH and inception of soot particles including (1) the reaction mechanism and kinetics of the resonance stabilized fulvenallenyl radical with propargyl and C 3 H 4 isomers; (2) the reaction mechanism and kinetics for the C + indene and C 2 + styrene reactions producing naphthyl or azulenyl radicals in low-temperature environments; (3) the MD study of non-equilibrium dimerization of acepyrene and coronene and its radical. The information derived from our theoretical calculations contributed to a better fundamental understanding of the reaction mechanisms and provide missing critical kinetic data to improve combustion models of hydrocarbon fuels and astrochemical models of the growth of carbonaceous molecules and particles in cold molecular clouds, circumstellar envelopes, and planetary atmospheres.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

The GNIRS instrument on the Gemini 8-­‐m telescope observed comet 103P/Hartley on 2010-­‐ Dec-­‐04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­‐absorbing C=C aromatic rings, and these rings have to be less than 50-­‐100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (≥10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­‐grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­‐processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­‐after precursors to the more robust and complex organics studied as Insoluble Organic Matter in carbonaceous chondrites. Aliphatic coatings on submicron grains, however, will not be observable in absorption because they are fairly transparent, nor do the aliphatic carbonaceous coatings produce the 3.4 micron emission band because the particles they are attached to are too large (too many vibration modes). We must probe the nano-­‐sized organic carriers that undergo substantive thermal fluctuations in cometary comae and emit at 3.3 3.4 micron. Observations of the 3.3 and 3.4 micron emission features contribute to characterizing the evolution of organics prior to their incorporation into cometary nuclei as well as their rapid evolution in cometary comae, which in turn contributes to deepening our understanding of the evolution of organics on the surfaces of asteroids and outer icy bodies in our solar system. Studying organics in comets contributes to understanding the formation and evolution pathways of ISM organics through to the formation of the robust insoluble organic matter in meteorites. A'Hearn, M.F., et al. 2011, Science, 332, 1396; Bockelee-­‐Morvan, D. et al. 1995, Icarus, 116, 18; De Gregorio, B.T., et al. 2010, GCA, 74, 4454; Dello Russo, N., et al. 2011, ApJ, 734, L8; Dischler et al. 1983, Solid State Communications, 48, 105; Flynn, G., et al. 2010a, LPSC, 41, #1079; Flynn, G., et al. 2010b, COSPAR, 38, F31-­‐0012-­‐10; Flynn, G., Wirick, S. 2011, LPSC, 42, #1856; Fomenkova, et al. 1994, GCA 58, 4503; Matrajt, G., et al. 2013, ApJ, 765, 145; Schutte, et al. 1993, ApJ, 415, 397; Wooden, D.H. et al. 2011, EPSC-­‐DPS, 1557; Wooden, D.H. et al. 2013, submitted.

Stardust samples↗

Forsterite and Olivine in Sahara-97210 (LL3.2) and Chainpur (LL3.4) Chondrules: Compositional Evolution and the Influence of Melting

It is generally accepted that chondrules contain relict grains that did not crystallize in situ, and that forsterite is one type of relict grain which is a likely precursor for chondrules. Chemically and morphologically similar forsterite is also found as "isolated grains", especially in carbonaceous chondrites. Using SIMS, we analyzed forsterite, ferrous overgrowths around forsterite, and coexisting normal olivine in 5 chondrules and 2 isolated grains in the Sahara-97210 ('Sahara") LL3.2 chondrite. We earlier used the same methods to study olivine in 3 Chainpur chondrules that contain relict forsterite. Our new data for Sahara provide additional insight into the processes affecting chondrules and their precursors.

Ruzicka, A.↗

A Laboratory-driven Multiscale Investigation of X-Ray Induced Mass Loss and Photochemical Evolution in Cosmic Carbon and Silicate Dust

We present the results of an integrated laboratory and modeling investigation into the impact of stellar X-rays on cosmic dust. Carbonaceous grains were prepared in a cooled (< 200 K) supersonic expansion from aromatic molecular precursors, and were later irradiated with 970 eV X-rays. Silicate (enstatite) grains were prepared via laser ablation, thermally annealed, and later irradiated with 500 eV X-rays. Infrared spectra of the 3.4 μm band of the carbon sample prepared with benzene revealed 84% ± 5% band area loss for an X-ray dose of 5.2 x 10 23 eV.cm -2 . Infrared spectra of the 8 -12 μm Si-O band of the silicate sample revealed band area loss up to 63% ± 5% for doses of 2.3 x 10 23 eV.cm -2 . A hybrid Monte Carlo particle trajectory approach was used to model the impact of X-rays and ensuing photoelectrons, Auger and collisionally ionized electrons through the bulk. As a result of x-ray ionization and ensuing Coulomb explosions on surface molecules, the calculated mass loss is 60% for the carbonaceous sample and 46% for the silicate sample, within a factor of 2 of the IR band loss, supporting an X-ray induced mass-loss mechanism. We apply the laboratory X-ray destruction rates to estimate the lifetimes of dust grains in protoplanetary disks surrounding 1 M ⊙ and 0.1 M ⊙ G and M stars. In both cases, X-ray destruction timescales are short (a few million years) at the disk surface, but are found to be much longer than typical disk lifetimes (≳10 Myr) over the disk bulk.

79 ASTRONOMY AND ASTROPHYSICS↗

Meteoritic evidence that graphite is rare in the interstellar medium

Carbonaceous material from several distinct astrophysical environments that has been identified in primitive meteorites is discussed. Most of this material is not well crystallized graphite, but ranges from kerogenlike macromolecular organic matter to poorly graphitized carbon. Of the small fraction of the carbonaceous material which is graphite, most may have resulted from the graphitization of macromolecular precursors in the solar nebula. Since graphite is more stable than those precursors, preexisting interstellar graphite should have survived in meteorites to at least the same extent as did other forms of carbon. It is concluded from this dearth of graphite that graphitic carbon was not a major component of the interstellar dust at the time of the formation of the solar system.

Nuth, J. A.↗

Aldehydes in hydrothermal solution - Standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures

Aldehydes are common in a variety of geologic environments and are derived from a number of sources, both natural and anthropogenic. Experimental data for aqueous aldehydes were taken from the literature and used, along with parameters for the revised Helgeson-Kirkham-Flowers (HKF) equations of state, to estimate standard partial molal thermodynamic data for aqueous straight-chain alkyl aldehydes at high temperatures and pressures. Examples of calculations involving aldehydes in geological environments are given, and the stability of aldehydes relative to carboxylic acids is evaluated. These calculations indicate that aldehydes may be intermediates in the formation of carboxylic acids from hydrocarbons in sedimentary basin brines and hydrothermal systems like they are in the atmosphere. The data and parameters summarized here allow evaluation of the role of aldehydes in the formation of prebiotic precursors, such as amino acids and hydroxy acids on the early Earth and in carbonaceous chondrite parent bodies.

Schulte, Mitchell D.↗

Chondritic Models of 4 Vesta: Comparison of Data from the Dawn Mission with Predicted Internal Structure and Surface Composition/Mineralogy

While the HEDs provide an extremely useful basis for interpreting data from the Dawn mission, there is no guarantee that they provide a complete vision of all possible crustal (and possibly mantle) lithologies that are exposed at the surface of Vesta. With this in mind, an alternative approach is to identify plausible bulk compositions and use mass-balance and geochemical modelling to predict possible internal structures and crust/mantle compositions and mineralogies. While such models must be consistent with known HED samples, this approach has the potential to extend predictions to thermodynamically plausible rock types that are not necessarily present in the HED collection. Nine chondritic bulk compositions are considered (CI, CV, CO, CM, H, L, LL, EH, EL). For each, relative proportions and densities of the core, mantle, and crust are quantified. This calculation is complicated by the fact that iron may occur in metallic form (in the core) and/or in oxidized form (in the mantle and crust). However, considering that the basaltic crust has the composition of Juvinas and assuming that this crust is in thermodynamic equilibrium with the residual mantle, it is possible to calculate a single solution to this problem for a given bulk composition. Of the nine bulk compositions tested, solutions corresponding to CI and LL groups predicted a negative metal fraction and were not considered further. Solutions for enstatite chondrites imply significant oxidation relative to the starting materials and these solutions too are considered unlikely. For the remaining bulk compositions, the relative proportion of crust to bulk silicate is typically in the range 15 to 20% corresponding to crustal thicknesses of 15 to 20 km for a porosity-free Vesta-sized body. The mantle is predicted to be largely dominated by olivine (greater than 85%) for carbonaceous chondrites, but to be a roughly equal mixture of olivine and pyroxene for ordinary chondrite precursors. All bulk compositions have a significant core, but the relative proportions of metal and sulphide can be widely different. Using these data, total core size (metal+ sulphide) and average core densities can be calculated, providing a useful reference frame within which to consider geophysical/gravity data of the Dawn mission. Further to these mass-balance calculations, the MELTS thermodynamic calculator has been used to assess to what extent chondritic bulk compositions can produce Juvinas-like liquids at relevant degrees of partial melting/crystallization. This work will refine acceptable bulk compositions and predict the mineralogy and composition of the associated solid and liquid products over wide ranges of partial melting and crystallization, providing a useful and self-consistent reference frame for interpretation of the data from the VIR and GRaND instruments onboard the Dawn spacecraft.

Toplis, M. J.↗

Internal Structure and Mineralogy of Differentiated Asteroids Assuming Chondritic Bulk Composition: The Case of Vesta

Bulk composition (including oxygen content) is a primary control on the internal structure and mineralogy of differentiated asteroids. For example, oxidation state will affect core size, as well as Mg# and pyroxene content of the silicate mantle. The Howardite-Eucrite-Diogenite class of meteorites (HED) provide an interesting test-case of this idea, in particular in light of results of the Dawn mission which provide information on the size, density and differentiation state of Vesta, the parent body of the HED's. In this work we explore plausible bulk compositions of Vesta and use mass-balance and geochemical modelling to predict possible internal structures and crust/mantle compositions and mineralogies. Models are constrained to be consistent with known HED samples, but the approach has the potential to extend predictions to thermodynamically plausible rock types that are not necessarily present in the HED collection. Nine chondritic bulk compositions are considered (CI, CV, CO, CM, H, L, LL, EH, EL). For each, relative proportions and densities of the core, mantle, and crust are quantified. Considering that the basaltic crust has the composition of the primitive eucrite Juvinas and assuming that this crust is in thermodynamic equilibrium with the residual mantle, it is possible to calculate how much iron is in metallic form (in the core) and how much in oxidized form (in the mantle and crust) for a given bulk composition. Of the nine bulk compositions tested, solutions corresponding to CI and LL groups predicted a negative metal fraction and were not considered further. Solutions for enstatite chondrites imply significant oxidation relative to the starting materials and these solutions too are considered unlikely. For the remaining bulk compositions, the relative proportion of crust to bulk silicate is typically in the range 15 to 20% corresponding to crustal thicknesses of 15 to 20 km for a porosity-free Vesta-sized body. The mantle is predicted to be largely dominated by olivine (>85%) for carbonaceous chondrites, but to be a roughly equal mixture of olivine and pyroxene for ordinary chondrite precursors. All bulk compositions have a significant core, but the relative proportions of metal and sulphide can be widely different. Using these data, total core size (metal+ sulphide) and average core densities can be calculated, providing a useful reference frame within which to consider geophysical/gravity data of the Dawn mission.

Toplis, M. J.↗

Low-Temperature Formation of Carbonaceous Grains from PAHs

Astronomical observations have detected interstellar carbon in the form of polycyclic aromatic hydrocarbons(PAHs) as well as carbonaceous dust, confirming its presence in both gaseous and solid phases. The goal of this study is to experimentally investigate low-temperature chemical pathways between these two phases in order to better understand the evolution of cosmic carbon. Cosmic dust analogs are produced in the supersonic expansion of an argon jet seeded with aromatic molecules: benzene, naphthalene, anthracene, phenanthrene, and pyrene. These are prototype aromatic molecules of compact and non compact structure, and are used to evaluate the effect of precursor structure on the molecular complexity of the resulting grains. The seeded jet is exposed to an electrical discharge and the carbonaceous grains are collected and probed ex situ via laser desorption mass spectrometry. Mass spectra reveal a rich molecular diversity within the grains, including fragments of the parent molecule but also growth into larger complex organic molecules (COMs). In all experiments, the largest number of products is found in the m/z range 200-250, and C16H10 (attributed to pyrene and/or its isomers) is found to be a dominant product, pointing at the formation of this stable PAH as a preferential route in the growth to larger PAHs. Comparison to mass spectra from the Murchison meteorite reveals a similar dominance of compounds related toC16H10 at m/z = 202. Evidence of the methyl addition-cyclization mechanism in the anthracene experiment is reported. PAH structure is found to impact the dust production yield, as seen by the greater yield for the anthracene compared to the phenanthrene experiment. PAH growth at low temperatures via barrierless routes involving the addition of alkyl- and phenyl-type radicals is suggested as a viable pathway to COMs. These results suggest that PAH growth and dust formation from PAHs are feasible at low temperatures in photon-dominated regions and circumstellar envelopes.

L Gavilan↗

Low Temperature Formation of Carbonaceous Grains from Hydrocarbons and PAHs with the COSmIC Facility

Complex carbon molecules and ions are ubiquitous in space and form the building blocks of the carbonaceous components of cosmic dust grains, ultimately contributing to the formation of planets. We report experimental investigations of the low temperature chemical pathways leading to the formation of cosmic grain analogs from gas phase molecular precursors to better understand the evolution of cosmic carbon. The study of the formation of dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. Although dust plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of carbonaceous dust. The experiments were performed using the Cosmic Simulation Chamber (COSmIC) to generate and characterize solid grains formed from gas phase precursors under controlled conditions representative of astrophysical environments [1]. Using COSmIC, it is possible to investigate the evolution of cosmic carbon from the formation of neutral and ionized hydrocarbons and PAHs in the gas phase [2], to solid carbon grains [3, 4, 5]. This is achieved by using a pulsed slit discharge nozzle to produce an adiabatic jet expansion and cool down Ar-hydrocarbon and PAH gas mixtures to astrophysically relevant temperature before inducing chemistry by generating a plasma discharge in the stream of the expansion. This plasma induced chemistry results in the formation of complex molecules and solid particles, analogs of cosmic grains in situ in the plasma expansion (i.e., without wall effects) that are carried by the accelerated gas in the expansion, and collected on substrates placed a few centimeters downstream of the electrodes. The results of a preliminary solid phase ex-situ analysis of cosmic grain analogs produced from a series of gas mixtures including hydrocarbons such as CH4 and C2H2 [3] and PAHs [4, 5] found in circumstellar ejecta of late C stars will be discussed. SEM imaging was used to provide insight on the impact of the precursors on the morphology and growth structure of the grains produced [3]. Laser desorption mass spectrometry was used to identify the molecules making up the main structures within the condensed grains [4] while X-ray irradiation and X-ray photoemission spectroscopy were used to investigate the impact the impact of stellar X-rays on cosmic dust.

Carbonaceous Grains↗

Deuterium Enrichment of Amino and Hydroxy Acids Found in the Murchison Meteorite: Constraints on Parent Body Conditions

The alpha-amino and alpha-hydroxy acids found in the Murchison carbonaceous chondrite are deuterium enriched. These compounds are thought to have originated from common deuterium enriched carbonyl precursors, by way of a Strecker synthesis which took place in a solution of HCN, NH3, and carbonyl compounds during the period of aqueous alteration of the meteorite parent body. However, the hydroxy acids found on Murchison are less deuterium enriched than the amino acids. With the objective of determining if the discrepancy in deuterium enrichment between the amino acids and the hydroxy acids found on Murchison is consistent with their formation in a Strecker synthesis, we have measured the deuterium content of alpha-amino and alpha-hydroxy acids produced in solutions of deuterated carbonyl compounds, KCN and NH4Cl, and also in mixtures of such solutions and Allende dust at 263 K and 295 K. Retention of the isotopic signature of the starting carbonyl by both alpha amino acids and alpha hydroxy acids is more dependent upon temperature, concentration and pH than upon the presence of meteorite dust in the solution. The constraints these observations place on Murchison parent body conditions will be discussed.

Lerner, Narcinda R.↗

Soot Precursor Material: Spatial Location via Simultaneous LIF-LII Imaging and Characterization via TEM

The chemical and physical transformation between gaseous fuel pyrolysis products and solid carbonaceous soot represents a critical step in soot formation. In this paper, simultaneous two-dimensional LIF-LII (laser-induced fluorescence - laser-induced incandescence) images identify the spatial location where the earliest identifiable chemical and physical transformation of material towards solid carbonaceous soot occurs along the axial streamline in a normal diffusion flame. The identification of the individual LIF and LII signals is achieved by examining both the excitation wavelength dependence and characteristic temporal decay of each signal. Spatially precise thermophoretic sampling measurements are guided by the LIF-LII images with characterization of the sampled material accomplished via both bright and dark field TEM. Both bright and dark field TEM measurements support the observed changes in photophysical properties which account for conversion of fluorescence to incandescence as fuel pyrolysis products evolve towards solid carbonaceous soot.

VanderWal, Randall L.↗

Amino Acid Degradation after Meteoritic Impact Simulation

Amino acids are among the most important prebiotic molecules as it is from these precursors that the building blocks of life were formed [1]. Although organic molecules were among the components of the planetesimals making up the terrestrial planets, large amounts of primitive organic precursor molecules are believed to be exogenous in origin and to have been imported to the Earth via micrometeorites, carbonaceous meteorites and comets, especially during the early stages of the formation of the Solar System [1,2]. Our study concerns the hypothesis that prebiotic organic matter, present on Earth, was synthesized in the interstellar environment, and then imported to Earth by meteorites or micrometeorites. We are particularly concerned with the formation and fate of amino acids. We have already shown that amino acid synthesis is possible inside cometary grains under interstellar environment conditions [3]. We are now interested in the effects of space conditions and meteoritic impact on these amino acids [4-6]. Most of the extraterrestrial organic molecules known today have been identified in carbonaceous chondrite meteorites [7]. One of the components of these meteorites is a clay with a composition close to that of saponite, used in our experiments. Two American teams have studied the effects of impact on various amino acids [8,9]. [8] investigated amino acids in saturated solution in water with pressure ranges between 5.1 and 21 GPa and temperature ranges between 412 and 870 K. [9] studied amino acids in solid form associated with and without minerals (Murchison and Allende meteorite extracts) and pressure ranges between 3 and 30 GPa. In these two experiments, the amino acids survived up to 15 GPa. At higher pressure, the quantity of preserved amino acids decreases quickly. Some secondary products such as dipeptides and diketopiperazins were identified in the [8] experiment.

Bertrand, M.↗