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NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗
NASA NTRS2020

Inter-species molecular attraction effect in the development of a two-species mixing layer

Simulations of fluid mixing occurring at high-pressures mandate the use of real-fluid equations of state to capture the effect of boh intermolecular repulsive forces and attractive forces which are neglected in perfect gases. Dedicated mixing rules account for these forces by providing a generic mapping of the mixture state-space onto a pure fluid domain. However, the specific inter-species molecular forces depend on the particular characteristics of the molecular pairs under consideration, and typically require the knowledge of binary interaction coefficients k_{αβ}. The impact of k_{αβ} on a flow field is as of now unclear; further, k_{αβ} is unknown for many molecular pairs and when unknown, set to be null. This study addresses the impact of k_{αβ} on the temporal evolution of a real-fluid mixing layer and uses Direct Numerical Simulation (DNS) to explore this impact. The results show differences between augmented attraction (k_{αβ}<0) and diminished attraction (k_{αβ}>0), affecting both fluid dynamics and diffusion processes. Specifically, in a binary mixing layer, it is observed that augmented attraction leads to delayed transition and mixing layer growth, manifested in the momentum layer thickness. The fractal dimension, which is a manifestation of interface corrugation, is calculated. These results provide an hitherto undocumented mechanism affecting the development of mixing layers.

Banuti, Daniel↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system has been guided by our under-standing of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure, and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-excesses of chiral amino acids or sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. However, studies of primitive meteorites have revealed that they contain extraterrestrial amino acids and sugar acids with large enantiomeric excesses (60% and higher) that resulted from non-biological processes [1], complicating the use of chiral asymmetry by itself as a definitive biosignature. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, is an objective of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite on Mars [2-5], NASA’s Curiosity rover has found evidence of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars [5], indigenous achiral amino acids have been identified in one martian meteorite [6]. It is expected that amino acid racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [7]. The ESA/Roscosmos ExoMars mission scheduled for launch next year includes the Rosalind Franklin rover designed to acquire samples from a depth of ~2 m and deliver them to a suite of instruments, including the Mars Organic Molecule Analyzer (MOMA). The MOMA instrument contains a wet chemistry experiment designed specifically for the detection of amino acids and measurement of their enantiomeric compositions [8]. The complexity and limited duration of spaceflight operations, and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic com-pounds in ancient rocks, make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, bulk and molecule-specific isotopic, and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars derives from bio-tic or abiotic processes. Ultimately, Mars Sample Return of rock cores collected by NASA’s Perseverance rover may be our best chance of identifying chemical biosignatures, including any chiral amino acid asymmetry resulting from a past or present martian biota, if one ever existed on Mars. Here we review our current knowledge of the distributions, and enantiomeric and isotopic com-positions of amino acids found in meteorites compared to terrestrial biochemistry. We also propose a set of measurement criteria that should be used to help establish the sources of any amino acids detected in samples returned from Mars using state-of-the-art gas and liquid chromatography mass spectrometry techniques [1].

D P Glavin↗
NASA NTRS2019

Chemical Ecosystem Selection on Mineral Surfaces Reveals Long-Term Dynamics Consistent with the Spontaneous Emergence of Mutual Catalysis

How did chemicals first become organized into systems capable of self-propagation and adaptive evolution? One possibility is that the first evolvers were chemical ecosystems localized on mineral surfaces and composed of sets of molecular species that could catalyze each other’s formation. We used a bottom-up experimental framework; chemical ecosystem selection (CES) to evaluate this perspective and search for surface-associated; and mutually catalytic chemical systems based on the changes in chemistry they are expected to induce. Here, we report the results of preliminary CES experiments conducted using a synthetic “prebiotic soup” and pyrite grains, which yield dynamical patterns that are suggestive of the emergence of mutual catalysis. While more research is needed to better understand the specific patterns observed here and determine whether they are reflective of self-propagation, these results illustrate the potential power of CES to test competing hypotheses for the emergence of protobiological chemical systems.

autocatalysis↗
NASA NTRS1990

Titan

Saturn's satellite Titan is the second-largest in the solar system. Its dense atmosphere is mostly molecular nitrogen with an admixture of methane, a surface pressure of 1.5 bars and a surface temperature of 94K. The fundamental driving force in the long-term evolution of Titan's atmosphere is the photolysis of methane in the stratosphere to form higher hydrocarbons and aerosols. The current rate of photolysis and undersaturation of methane in the lower troposphere suggests the presence of a massive ethane-methane-nitrogen ocean. The ocean evolves to a more ethane-rich state over geologic time, driving changes in the atmospheric thermal structure. An outstanding issue concerning Titan's earliest history is the origin of atmospheric nitrogen: was it introduced into Titan as molecular nitrogen or ammonia? Measurement of the argon-to-nitrogen ratio in the present atmosphere provides a diagnostic test of these competing hypotheses. Many of the questions raised by the Voyager encounters about Titan and its atmosphere can be adequately addressed only by an entry probe, such as that planned for the Cassini mission.

Lunine, Jonathan I.↗
NASA NTRS1973

A review of processable high temperature resistant addition-type laminating resins

An important finding that resulted from research that was conducted to develop improved ablative resins was the discovery of a novel approach to synthesize processable high temperature resistant polymers. Low molecular weight polyimide prepolymers end-capped with norbornene groups were polymerized into thermo-oxidatively stable modified polyimides without the evolution of void producing volatile materials. This paper reviews basic studies that were performed using model compounds to elucidate the polymerization mechanism of the so-called addition-type polyimides. The fabrication and properties of polyimide/graphite fiber composites using A-type polyimide prepolymer as the matrix are described. An alternate method for preparing processable A-type polyimides by means of in situ polymerization of monomeric reactants on the fiber reinforcement is also described. Polyimide/graphite fiber composite performance at elevated temperatures is presented for A-type polyimides.

Serafini, T. T.↗
NASA NTRS1985

Evolution of Titan's coupled ocean-atmosphere system and interaction of ocean with bedrock

A recent model for the surface state of Titan proposes a liquid ethane-methane-molecular nitrogen layer of order one kilometer thick which because of stratospheric methane photolysis has become increasingly ethane-rich with time. The interaction of such an ocean with the underlying 'bedrock' of Titan (assumed to be water-ice or ammonia hydrate) and with the primarily nitrogen atmosphere is explored. It is concluded that although modest exchange of oceanic hydrocarbons with enclathrated methane in the bedrock can in principle occur, it is unlikely for reasonable regolith depths. The surprisingly high solubility of water-ice in liquid methane implies that topographic features on Titan of order 100 meters in height can be eroded away on a time scale of one-billion years. The large solubility difference of N2 in methane versus ethane implies that the ocean composition is a strong determinant of atmospheric pressure; a simple radiative model of the Titan atmosphere is employed to demonstrate that significant surface pressure and temperature changes can occur as the oceanic composition evolves with time.

Lunine, J. I.↗
NASA NTRS1989

Origin and evolution of outer solar system atmospheres

The origin and evolution of the atmospheres of bodies in the outer solar system is studied on the basis of the abundances of key molecular species. Formation models in which significant infall of icy and rocky planetesimals accompanies planet formation is supported by the enrichment of methane and deuterated species from Jupiter and Neptune. The chemistry of the solar nebula and Titan are discussed. The prospects for obtaining information on the atmosphere of Triton from the Voyager 2 mission are considered. It is found that the mean density of the Pluto-Charon system implies an origin in the rather water-poor solar nebula.

Lunine, J. I.↗
NASA NTRS1993

The formation of protostellar disks. I - 1 M(solar)

Hydrodynamical calculations of the collapse of an axisymmetric, rotating one solar mass protostellar cloud, including the effects of radiative transfer and radiative acceleration but without magnetic fields, are presented. The results include calculations of infrared protostellar spectra as a function of time and viewing angle. A numerical algorithm involving explicit nested grids is used to resolve the region of initial disk formation and at the same time to include the outer regions in the calculation. The central part of the protostar is modeled approximately. Initial conditions are systematically varied to investigate their influence on the evolution and final configuration of central star plus circumstellar disk. The initial state for the standard case is a centrally condensed molecular cloud core of one solar mass with a mean density of 8 x 10 exp -18 g/cu cm and a specific angular momentum at the outer edge of 7 x 10 exp 20 sq cm/s. The collapse is followed for 8 x 10 exp 4 yr, at which point 0.45 solar mass is contained in a rapidly rotating central object and most of the remainder in a surrounding equilibrium disk. The stability of this final structure is qualitatively analyzed.

Yorke, Harold W.↗
NASA NTRS2008

Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

Cooper, Paul D.↗
NASA NTRS2016

The Star Formation Rate Efficiency of Neutral Atomic-Dominated Hydrogen Gas in the Ooutskirts of Star-Forming Galaxies From z approx. 1 to z approx. 3

Current observational evidence suggests that the star formation rate (SFR)efficiency of neutral atomic hydrogen gas measured in damped Ly(alpha) systems (DLAs) at z approx. 3 is more than 10 times lower than predicted by the Kennicutt-Schmidt (KS)relation. To understand the origin of this deficit, and to investigate possible evolution with redshift and galaxy properties, we measure the SFR efficiency of atomic gas at z approx. 1, z approx. 2, and z approx. 3 around star-forming galaxies. We use new robust photometric redshifts in the Hubble Ultra Deep Field to create galaxy stacks in these three redshift bins, and measure the SFR efficiency by combining DLA absorber statistics with the observed rest-frame UV emission in the galaxies' outskirts. We find that the SFR efficiency of H I gas at z > 1 is approx. 1%-3% of that predicted by the KS relation. Contrary to simulations and models that predict a reduced SFR efficiency with decreasing metallicity and thus with increasing redshift, we find no significant evolution in the SFR efficiency with redshift. Our analysis instead suggests that the reduced SFR efficiency is driven by the low molecular content of this atomic-dominated phase, with metallicity playing a secondary effect in regulating the conversion between atomic and molecular gas. This interpretation is supported by the similarity between the observed SFR efficiency and that observed in local atomic-dominated gas, such as in the outskirts of local spiral galaxies and local dwarf galaxies.

Rafelski, Marc↗
NASA NTRS2022

GJ 229B: Solving the Puzzle of the First Known T Dwarf with the APOLLO Retrieval Code

GJ 229B was the first T dwarf to be discovered in 1995, and its spectrum has been more thoroughly observed than that of most other brown dwarfs. Yet a full spectroscopic analysis of its atmosphere has not been done with modern techniques. This spectrum has several peculiar features, and recent dynamical estimates of GJ 229B’s mass and orbit have disagreed widely, both of which warrant closer investigation. With a separation of tens of astronomical units from its host star, GJ 229B falls near the border of the planet and stellar population formation regimes, so its atmosphere could provide clues to formation processes for intermediate objects of this type. In an effort to resolve these questions, we performed retrievals on published spectra of GJ 229B over a wide range of wavelengths (0.5–5.1 μm) using the open-source APOLLO code. Based on these retrievals, we present a more precise mass estimate of 41.6 ± 3.3MJ and an effective temperature estimate of 869 +5 −7 K, which are more consistent with evolutionary models for brown dwarfs and suggest an older age for the system of >1.0 Gyr. We also present retrieved molecular abundances for the atmosphere, including replicating the previously observed high CO abundance, and discuss their implications for the formation and evolution of this object. This retrieval effort will give us insight into how to study other brown dwarfs and directly imaged planets, including those observed with JWST and other next-generation telescopes.

Alex R Howe↗
NASA NTRS1986

Chemical evolution in spiral and irregular galaxies

A brief review of models of chemical evolution of the interstellar medium in our galaxy and other galaxies is presented. These models predict the time variation and radial dependence of chemical composition in the gas as function of the input parameters; initial mass function, stellar birth rate, chemical composition of mass lost by stars during their evolution (yields), and the existence of large scale mass flows, like infall from the halo, outflow to the intergalactic medium or radial flows within a galaxy. At present there is a considerable wealth of observational data on the composition of HII regions in spiral and irregular galaxies to constrain the models. Comparisons are made between theory and the observed physical conditions. In particular, studies of helium, carbon, nitrogen and oxygen abundances are reviewed. In many molecular clouds the information we have on the amount of H2 is derived from the observed CO column density, and a standard CO/H2 ratio derived for the solar neighborhood. Chemical evolution models and the observed variations in O/H and N/O values, point out the need to include these results in a CO/H2 relation that should be, at least, a function of the O/H ratio. This aspect is also discussed.

Torres-Peimbert, S.↗
NASA NTRS2005

Ion Neutral Mass Spectrometer Measurements from Titan

Introduction: The Ion Neutral Mass Spectrometer (INMS) aboard the Cassini orbiter has obtained the first in situ composition measurements of the neutral densities of molecular nitrogen, methane, argon, and a host of stable carbon-nitrile compounds in its first flyby of Titan. The bulk composition and thermal structure of the moon s upper atmosphere do not appear to be changed since the Voyager flyby in 1979. However, the more sensitive techniques provided by modern in-situ mass spectrometry also give evidence for large-spatial-scale large-amplitude atmospheric waves in the upper atmosphere and for a plethora of stable carbon-nitrile compounds above 1174 km. Furthermore, they allow the first direct measurements of isotopes of nitrogen, carbon, and argon, which provide interesting clues about the evolution of the atmosphere. The atmosphere was first accreted as ammonia and ammonia ices from the Saturn sub-nebula. Subsequent photochemistry likely converted the atmosphere into molecular nitrogen. The early atmosphere was 1.5 to 5 times more substantial and was lost via escape over the intervening 4.5 billion years due to the reduced gravity associated with the relatively small mass of Titan. Carbon in the form of methane has continued to outgas over time from the interior with much of it being deposited in the form of complex hydrocarbons on the surface and some of it also being lost to space.

Waite, J. H., Jr.↗
NASA NTRS1995

Chemical evolution of circumstellar matter around young stellar objects

Recent observational studies of the chemical composition of circumstellar matter around both high- and low-mass young stellar objects are reviewed. The molecular abundances are found to be a strong function of evolutionary state, but not of system mass or luminosity. The data are discussed with reference to recent theoretical models.

Non-NASA Center↗
NASA NTRS2000

Laboratory investigation of the contribution of complex aromatic/aliphatic polycyclic hybrid molecular structures to interstellar ultraviolet extinction and infrared emission

We have demonstrated by experiment that, in an energetic environment, a simple polycyclic aromatic hydrocarbon (PAH) such as naphthalene will undergo chemical reactions that produce a wide array of more complex species (an aggregate). For a stellar wind of a highly evolved star (post-asymptotic giant branch [post-AGB]), this process would be in addition to what is expected from reactions occurring under thermodynamic equilibrium. A surprising result of that work was that produced in substantial abundance are hydrogenated forms that are hybrids of polycyclic aromatic and polycyclic alkanes. Infrared spectroscopy described here reveals a spectral character for these materials that has much in common with that observed for the constituents of circumstellar clouds of post-AGB stars. It can be demonstrated that a methylene (-CH2-) substructure, as in cycloalkanes, is the likely carrier of the 6.9 microns band emission of dust that has recently been formed around IRAS 22272+5433, NGC 7027, and CPD -56 8032. Ultraviolet spectroscopy previously done with a lower limit of 190 nm had revealed that this molecular aggregate can contribute to the interstellar extinction feature at 2175 angstroms. We have now extended our UV spectroscopy of these materials to 110 nm by a vacuum ultraviolet technique. That work, described here, reveals new spectral characteristics and describes how material newly formed during the late stages of stellar evolution could have produced an extinction feature claimed to exist at 1700 angstroms in the spectrum of HD 145502 and also how the newly formed hydrocarbon material would be transformed/aged in the general interstellar environment. The contribution of this molecular aggregate to the rise in interstellar extinction at wavelengths below 1500 angstroms is also examined. The panspectral measurements of the materials produced in the laboratory, using plasmas of H, He, N, and O to convert the simple PAH naphthalene to an aggregate of complex species, provide insight into possible molecular structure details of newly formed hydrocarbon-rich interstellar dust and its transformation into aged material that becomes resident in the interstellar medium. Specifically the presence of naphthalene-like and butadiene-like conjugated structures as chromophores for the 2175 angstroms ultraviolet extinction feature is indicated.

NASA Discipline Exobiology↗