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Observations of the Infrared Solar Spectrum from Space by the ATMOS Experiment

The final flight of the Atmospheric Trace Molecule Spectroscopy experiment as part of the Atmospheric na Laboratory for Applications and Science (ATLAS-3) Space Shuttle mission in 1994 provided a new opportunity to measure broadband 625-4800/ cm, 2.1 - 16 micron infrared solar spectra at an unapodized resolution of 0.0l/ cm from space. The majority of the observations were obtained as exoatmospheric, of near Sun center, absorption spectra, which were later ratioed to grazing atmospheric measurements to compute the atmospheric transmission of the Earth's atmosphere and analyzed for vertical profiles of minor and trace gases. Relative to the SPACELAB-3 mission that produced 4800 high Sun spectra (which were averaged into four grand average spectra), the ATLAS-3 mission produced some 40,000 high Sun spectra (which have been similarly averaged) with an improvement in signal-to-noise ratio of a factor of 3-4 in the spectral region between 1000 and 4800/ cm. A brief description of the spectral calibration and spectral quality is given as well as the location of electronic archives of these spectra.

Abrams, M. C.↗

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↗

Evaluation of the Interference of Tenax®TA Adsorbent With Dimethylformamide Dimethyl Acetal Reagent for Gas Chromatography-Dragonfly Mass Spectrometry and Future Gas Chromatography-Mass Spectrometry in Situ Analysis

Among future space missions, national aeronautics and space administration (NASA) selected two of them to analyze the diversity in organic content within Martian and Titan soil samples using a gas chromatograph – mass spectrometer (GC–MS) instrument. The Dragonfly space mission is planned to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for years. One of the main goals of this mission is to understand the past and actual abundant prebiotic chemistry on Titan, which is not well characterized yet. The ExoMars space mission is planned to be launched in 2028 to Mars’ surface and explore the Oxia Planum and Mawrth Vallis region for years. The main objectives focus on the exploration of the subsurface soil samples, potentially richer in organics, that might be relevant for the search of past life traces on Mars where irradiation does not impact the matrices and organics. One recently used sample pre-treatment for gas chromatography – mass spectrometry analysis is planned on both space missions to detect refractory organic molecules of interest for astrobiology. This pre-treatment is called derivatization and uses a chemical reagent – called dimethylformamide dimethyl acetal (DMF-DMA) – to sublimate organic compounds keeping them safe from thermal degradation and conserving the chirality of the molecules extracted from Titan or Mars’ matrices. Indeed, the detection of building blocks of life or enantiomeric excess of some organics (e.g. amino acids) after DMF-DMA pre-treatment and GC–MS analyses would be both bioindicators. The main results highlighted by our work on DMF-DMA and Tenax®TA interaction and efficiency to detect organic compounds at ppb levels in a fast and single preparation are first that Tenax®TA did not show the onset of degradation until after 150 experiments – a 120 h at 300 °C experiment – which greatly exceeds the experimental lifetimes for the DraMS and GC-space in situ investigations. Tenax®TA polymer and DMF-DMA produce many by-products (about 70 and 46, respectively, depending on the activation temperature). Further, the interaction between the two leads to the production of 22 additional by-products from DMF-DMA degradation, but these listed by-products do not prevent the detection of trace-level organic molecules after their efficient derivatization and volatilization by DMF-DMA in the oven ahead the GC–MS trap and column.

DraMS-Dragonfly mission↗

Ice Radiation Chemistry as a Source of Potential False Biomarkers on the Surface of Europa

If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While molecules such as amino acids and nucleo-bases might seem to be biomarkers, and alkyl substituted aromatics have been invoked as such, they are not necessarily. These molecules are present in some meteorites and are expected to be present on the surface of other planets even in the absence of life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for true biomarkers on other worlds. Our experiments have shown that some organic molecules in meteorites that appear biological in nature are formed by energetic processing of extraterrestrial ices can account for amino acids, quinones and other functionalized aromatic compounds. In the past, such molecules have been proposed as biomarkers. For example, alkylated aromatics were invoked as biomarkers in the Alan Hills 84001 'Martian meteorite.' When simple organics arrive at the surface of a body like Europa, either from below or from space, how long do they survive and what do they make? How can we distinguish these from real biomarkers?

Bernstein, Max P.↗

Low-Temperature Production of Cosmic Grains Analogs From Gas-Phase Molecular Precursors with the NASA Ames' COSmIC Facility

Complex carbon molecules and ions are ubiquitous in space and form the building blocks of carbonaceous cosmic dust grains, ultimately contributing to the formation of planets. Here, we report the first experimental investigations of the low temperature chemical pathways leading to the production of cosmic grain analogs from gas phase molecular precursors in order to better understand the evolution of cosmic carbon. The experiments were performed using the COsmic SImulation Chamber (COSmIC) to generate and characterize 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 gas phase hydrocarbons and PAHs [2], to carbon grains [3, 4]. This is achieved by using a discharge nozzle to (1) produce an adiabatic jet expansion and cool down Ar-hydrocarbon/PAH gas mixtures to astrophysically relevant temperature (150 K) 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. Solid grains are produced in-situ in the plasma expansion, 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 at low temperature in COSmIC from gas mixtures including molecular precursors of cosmic carbon grains, i.e., such as CH4 and C2H2 found in circumstellar ejecta of late C stars [3] as well as PAHs ubiquitously detected in IR emission bands seen in galactic and extragalactic environments [4] will be discussed. Scanning Electron Microscopy imaging was used to provide insight on the morphology and growth structure of the grains produced in COSmIC, and to investigate how the precursors used to produce the grains affect these parameters [3]. Laser desorption mass spectrometry was used to identify the molecules making up the main structures within the condensed grains [4]. NIR to FIR optical properties are characterized to provide critical information (functional groups, optical constants) to the scientific community, for use in radiative transfer models in particular, and to help decipher and enhance the return data from space observations.

F. Salama↗

The Role of Grain Surface Reactions in the Chemistry of Star Forming Regions

The importance of reactions at the surfaces of dust grains has long been recognized to be one of the two main chemical processes that form molecules in cold, dark interstellar clouds where simple, saturated (fully-hydrogenated) molecules such as H2 water, methanol, H2CO, H2S, ammonia and CH4 are present in quantities far too high to be consistent with their extremely low gas phase formation rates. In cold dark regions of interstellar space, dust grains provide a substrate onto which gas-phase species can accrete and react. Grains provide a "third body" or a sink for the energy released in the exothermic reactions that form chemical bonds. In essence, the surfaces of dust grains open up alternative reaction pathways to form observed molecules whose abundances cannot be explained with gas-phase chemistry alone. This concept is taken one step further in this work: instead of merely acting as a substrate onto which radicals and molecules may physically adsorb, some grains may actively participate in the reaction itself, forming chemical bonds with the accreting species. Until recently, surface chemical reactions had not been thought to be important in warm circumstellar media because adspecies rapidly desorb from grains at very low temperatures; thus, the residence times of molecules and radicals on the surface of grains at all but the lowest temperatures are far too short to allow these reactions to occur. However, if the adspecies could adsorb more strongly, via a true chemical bond with surfaces of some dust grains, then grain surface reactions will play an important role in warm circumstellar regions as well. In this work, the surface-catalyzed reaction CO + 3 H2 yields CH4 + H2O is studied in the context that it may be very effective at converting the inorganic molecule CO into the simplest organic compound, methane. H2 and CO are the most abundant molecules in space, and the reaction converting them to methane, while kinetically inhibited in the gas phase under most astrophysical conditions, is catalyzed by iron, an abundant constituent of interstellar dust. At temperatures between 600 and 1000 K, which occur in the outflows from red giants and near luminous young stars, this reaction readily proceeds in the presence of an iron catalyst. Iron is one of the more abundant elements composing interstellar dust. Its abundance relative to hydrogen is almost that of silicon, and both of these heavy elements are primarily locked up in dust at all but the hottest regions of interstellar space.

Kress, M. E.↗

A spectroscopic experimental and computer-assisted empirical model for the production and energetics of excited oxygen molecules formed by atom recombination on shuttle tile surfaces

A visible emission spectroscopic method was developed. The amounts of excited singlet and triplet oxygen molecules produced by recombination on the Space Shuttle Orbiter thermal protective tiles at elevated temperatures are determined. Rate constants and energetics of the extremely exothermic reaction are evaluated in terms of a chemical and mathematical model. Implications for potential contribution to Shuttle surface reentry heating fluxes are outlined.

Owan, D. A.↗

Tunable laser heterodyne spectrometer measurements of atmospheric species

It is pointed out that spectroscopic measurements conducted with the aid of tunable laser heterodyne spectrometers in the 3-30 micron range of the electromagnetic spectrum have the potential to measure the vertical profiles of tenuous gas molecules in the atmosphere with ultra high spectral resolution and great sensitivity. Programs related to the realization of this potential have been conducted for some time, and a Laser Heterodyne Spectrometer (LHS) experiment was developed. The present investigation has the objective to provide an overview of the LHS concept for measuring the vertical profiles of tenuous gas molecules in the upper atmosphere from space and airborne platforms, and to discuss the sensitivity ranges for this technique.

Allario, F.↗

Synthesis, Characterization and Decomposition Studies of Tris(N,N-dibenzyldithiocarbamato) Indium(III): Chemical Spray Deposition of Polycrystalline CuInS2 on Copper Films

Tris(bis(phenylmethyl)carbamodithioato-S,S ), commonly referred to as tris(N,Ndibenzyldithiocarbamato) indium(III), In(S2CNBz2)3, was synthesized and characterized by single crystal X-ray crystallography. The compound crystallizes in the triclinic space group P1 bar with two molecules per unit cell. The material was further characterized using a novel analytical system employing the combined powers of thermogravimetric analysis, gas chromatography/mass spectrometry and Fourier-Transform infrared spectroscopy to investigate its potential use as a precursor for the chemical vapor deposition (CVD) of thin film materials for photovoltaic applications. Upon heating, the material thermally decomposes to release CS2 and benzyl moieties in to the gas phase, resulting in bulk In2S3. Preliminary spray CVD experiments indicate that In(S2CNBz2)3 decomposed on a Cu substrate reacts to produce stoichiometric CuInS2 films.

Hehemann, David G.↗

First Satellite Observations of Lower Tropospheric Ammonia and Methanol

The Tropospheric Emission Spectrometer (TES) on the EOS Aura satellite makes global measurements of infrared radiances which are used to derive profiles of species such as O3, CO, H2O, HDO and CH4 as routine standard products. In addition, TES has a variety of special modes that provide denser spatial mapping over a limited geographical area. A continuous-coverage mode (called ''transect'', about 460 km long) has now been used to detect additional molecules indicative of regional air pollution. On 10 July 2007 at about 05:37 UTC (13:24 LMST) TES conducted such a transect observation over the Beijing area in northeast China. Examination of the residual spectral radiances following the retrieval of the TES standard products revealed surprisingly strong features attributable to enhanced concentrations of ammonia (NH3) and methanol (CH3OH), well above the normal background levels. This is the first time that these molecules have been detected in space-based nadir viewing measurements that penetrate into the lower atmosphere.

methanol↗

A Flux-Pinning Mechanism for Segment Assembly and Alignment

Currently, the most compelling astrophysics questions include how planets and the first stars formed and whether there are protostellar disks that contain large organic molecules. Although answering these questions requires space telescopes with apertures of at least 10 meters, such large primaries are challenging to construct by scaling up previous designs; the limited capacity of a launch vehicle bounds the maximum diameter of a monolithic primary, and beyond a certain size, deployable telescopes cannot fit in current launch vehicle fairings. One potential solution is connecting the primary mirror segments edgewise using flux-pinning mechanisms, which are analogous to non-contacting damped springs. In the baseline design, a flux-pinning mechanism consists of a magnet and a superconductor separated by a predetermined gap, with the damping adjusted by placing aluminum near the interface. Since flux pinning is possible only when the superconductor is cooled below a critical temperature, flux-pinning mechanisms are uniquely suited for cryogenic space telescopes. By placing these mechanisms along the edges of the mirror segments, a primary can be built up over time. Since flux pinning requires no mechanical deployments, the assembly process could be robotic or use some other non-contacting scheme. Advantages of this approach include scalability and passive stability.

Gersh-Range, Jessica A.↗

Synthesis, Characterization, and Processing of Copper, Indium, and Gallium Dithiocarbamates for Energy Conversion Applications

Ten dithiocarbamate complexes of indium(III) and gallium(III) have been prepared and characterized by elemental analysis, infrared spectra and melting point. Each complex was decomposed thermally and its decomposition products separated and identified with the combination of gas chromatography/mass spectrometry. Their potential utility as photovoltaic materials precursors was assessed. Bis(dibenzyldithiocarbamato)- and bis(diethyldithiocarbamato)copper(II), Cu(S2CN(CH2C6H5)2)2 and Cu(S2CN(C2H5)2)2 respectively, have also been examined for their suitability as precursors for copper sulfides for the fabrication of photovoltaic materials. Each complex was decomposed thermally and the products analyzed by GC/MS, TGA and FTIR. The dibenzyl derivative complex decomposed at a lower temperature (225-320 C) to yield CuS as the product. The diethyl derivative complex decomposed at a higher temperature (260-325 C) to yield Cu2S. No Cu containing fragments were noted in the mass spectra. Unusual recombination fragments were observed in the mass spectra of the diethyl derivative. Tris(bis(phenylmethyl)carbamodithioato-S,S'), commonly referred to as tris(N,N-dibenzyldithiocarbamato)indium(III), In(S2CNBz2)3, was synthesized and characterized by single crystal X-ray crystallography. The compound crystallizes in the triclinic space group P1(bar) with two molecules per unit cell. The material was further characterized using a novel analytical system employing the combined powers of thermogravimetric analysis, gas chromatography/mass spectrometry, and Fourier transform infrared (FT-IR) spectroscopy to investigate its potential use as a precursor for the chemical vapor deposition (CVD) of thin film materials for photovoltaic applications. Upon heating, the material thermally decomposes to release CS2 and benzyl moieties in to the gas phase, resulting in bulk In2S3. Preliminary spray CVD experiments indicate that In(S2CNBz2)3 decomposed on a Cu substrate reacts to produce stoichiometric CuInS2 films.

Duraj, S. A.↗

The Role of Extraterrestrial Materials in the Origin of Life

It has been well established for some time now that C-rich organic materials are relatively common in a number of environments in space. This is known through the telescopic detection of these materials using spectroscopy techniques in the infrared and sub-millimeter wavelength ranges and through the identification of organics in extraterrestrial materials. Extraterrestrial materials in which organics have been found include collected meteorites and interplanetary dust particles, and samples returned by NASA spacecraft from comets. These organics are produced by a variety of astrochemical processes. Despite their abiotic origins, these organic materials of are considerable interest to astrobiology for several reasons. First, organic materials of any composition are important as a means of delivering the elements C, H, O, and N to the surfaces of newly formed planets, and these elements are likely critical to the origin and subsequent evolution of life (certainly for life as we know it). In addition, it is clear that at least a portion of the organics found in space are in the form of molecules that play important roles in modern biology - for example, molecules like amino acids, amphiphiles, quinones, etc. Thus, the delivery of extraterrestrial organics to planetary surfaces brings not only bulk C, H, O, and N, but also molecular complexity in forms that are potentially useful for the origin and early evolution of life. This suggests that the production and delivery of cosmic organic compounds may have played key roles in the origin of life on Earth and, by extension, on other planets in the universe.

Astrochemistry↗

Forecasting Rates of Volcanic Activity on Terrestrial Exoplanets and Implications for Cryovolcanic Activity on Extrasolar Ocean Worlds

Like the planets and moons in our solar system, the surfaces of terrestrial exoplanets may be shaped by volcanic activity. The magnitudes and rates of volcanic activity on terrestrial exoplanets will be intimately linked to their sizes and internal heating rates and can either facilitate or preclude the existence of habitable environments. In order to place bounds on the potential for such activity, we estimate total internal heating rates for 53 exoplanets with masses and radii up to∼8M⊕and 2R⊕, respectively, assuming that internal heating is drawn from both radiogenic and tidal sources. We then compare these internal heating rates to those of the planets and moons in our solar system in an attempt to constrain the expected rates of volcanic activity on these extrasolar worlds. We find that all 53 of the exoplanets surveyed are likely to have volcanic activity at their surfaces, and that at least 26% of these planets may be extrasolar ocean worlds. The majority of these ocean worlds may be similar in structure to the icy moons of the giant planets, having internal oceans beneath layers of surface ice. If so, these planets may exhibit cryovolcanism (i.e., icy volcanism)at their surfaces. Recent studies have shown that extrasolar volcanism could be detected by high-resolution spectrographs on existing ground-based telescopes. In the case of planets with densities and/or effective temperatures that are consistent with H2O-rich compositions, spectral identification of excess water vapor and other molecules that are explosively vented into space during cryovolcanic eruptions could serve as a way to infer the presence of subsurface oceans, and therefore indirectly assess their habitability. Considering the implications for habitability, our results suggest that continued characterization of terrestrial exoplanets in terms of their potential for volcanic activity should be a priority in the coming years.

Lynnae C Quick↗

Calculation of Thermochemical Properties of Carbon-cluster Ablation Species

Carbon clusters and hydrocarbons are constituents of the pyrolysis gases injected into the boundary layer of a space vehicle with a carbonaceous heat shield. These molecules have absorption spectra in the VUV and UV region that match the emission spectra of atomic nitrogen and oxygen. Hence, they can potentially absorb the radiation impinging on the heat shield of the space vehicle. This paper studies the ground state thermochemical properties and low-lying excited electronic states of potential radiation absorbing molecules present in the boundary layer using ab initio quantum chemistry methods. These results provide a more accurate prediction of the radiative heat flux on the surface which can lead to improvement in the design of the thermal protection system.

enthalpy↗

Let Dependent Low Dose and Synergistic Inhibition of Human Angiogenesis by Charged Particles: Validation of Micrornas That Drive Inhibition

The microvasculature permeates all tissues at the microscopic level making the whole body a target for Space Radiation. Depending on the trajectory a single heavy ion particle would traverse many micro-vessels as it passes through the body causing a widespread response. Studies on the effects of charged particles on the development of human 3D micro-vessel models show that angiogenesis is inhibited by all ions detectible at a dose of 1.25c Gy. However, there are two distinct mechanisms of inhibition depending on the linear energy transfer (LET). We show here that the inhibition of angiogenesis is demarcated into two groups. The blockage of the early motile stage of micro-vessel development occurs after exposure to light ions (LET 3 KeV/n or lower) whereas the prevention of the later stages of development when the microvessels widen into tubes occurs after exposure to heavy ions (LET 8 KeV/n or higher). Strikingly, the combined effect of each ion has a synergistic effect detectible as low as 0.6 cGy. The low fluence of these doses indicates a bystander effect where the response is transmitted to other cells by the secretion of molecules by targeted cells. Prime candidates are microRNAs (miRNAs) and we have previously identified three angiogenesis-associated miRNA regulators from serum, cardiac tissue, and micro-vessels exposed to a simplified Galactic Cosmic Radiation (GCR) simulation – a mixture of heavy and light ions found in Space. Synthetic molecules (Antagomirs) designed to inhibit the predicted miRNAs were successfully used to reverse the inhibition of angiogenesis by Space Radiation. With the simple application of the antagomirs as a countermeasure we have for the first time shown an amelioration of the complex response(s) of angiogenesis to Space Radiation. This opens a new avenue of possible mitigation strategies based on the regulation and understanding of master regulators. These results not only have impact with Space Radiation research, but also provide clues of possible therapeutics for terrestrial diseases in the clinical setting.

Yen-Ruh Wuu↗

Lunar utilization

The resources, techniques, and purposes to which lunar materials could be put are discussed, with attention given to transporting lunar materials to cislunar space for the construction of space manufacturing and habitable facilities. A model molecule, demandite, which represents the mole fraction of all materials used in the U.S. in 1967, is used to assess the lunar resources defined during Apollo missions. It is shown that duplication of the same manufacturing, fuel, and life-support systems in space as those on earth would cost several orders of magnitude more if the materials originated on earth than on the moon. The demandite would be sent into cislunar orbit using linear electric motors. Lunar surface concentrations of pyroxenes, olivine, feldspars, ilmenite, basalts, anorthostatic rocks, and breccias are reviewed, noting that carbon in the regolith is solar-wind derived, while in lunar rocks the carbon is indigenous. Lunar mining techniques are envisioned, especially the capacity to move large masses at 1/6 the effort required on the earth.

Waldron, R. D.↗

STS-40 orbital acceleration research experiment flight results during a typical sleep period

The Orbital Acceleration Research Experiment (OARE), an electrostatic accelerometer package with complete on-orbit calibration capabilities, was flown for the first time aboard the Space Shuttle on STS-40. This is also the first time an accelerometer package with nano-g sensitivity and a calibration facility has flown aboard the Space Shuttle. The instrument is designed to measure and record the Space Shuttle aerodynamic acceleration environment from the free molecule flow regime through the rarified flow transition into the hypersonic continuum regime. Because of its sensitivity, the OARE instrument defects aerodynamic behavior of the Space Shuttle while in low-earth orbit. A 2-hour orbital time period on day seven of the mission, when the crew was asleep and other spacecraft activities were at a minimum, was examined. During the flight, a 'trimmed-mean' filter was used to produce high quality, low frequency data which was successfully stored aboard the Space Shuttle in the OARE data storage system. Initial review of the data indicated that, although the expected precision was achieved, some equipment problems occurred resulting in uncertain accuracy. An acceleration model which includes aerodynamic, gravity-gradient, and rotational effects was constructed and compared with flight data. Examination of the model with the flight data shows the instrument to be sensitive to all major expected low frequency acceleration phenomena; however, some erratic instrument bias behavior persists in two axes. In these axes, the OARE data can be made to match a comprehensive atmospheric-aerodynamic model by making bias adjustments and slight linear corrections for drift. The other axis does not exhibit these difficulties and gives good agreement with the acceleration model.

Blanchard, R. C.↗