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All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Evolution of the Earth and Origin of Life: The Role of Gas/Fluid Interactions with Rocks

The work under the Cooperative Agreement will be centered on questions of the evolution of Life on the early Earth and possibly on Mars. It is still hotly debated whether the essential organic molecules were delivered to the early Earth from space (by comets, meteorites or interplanetary dust particles) or were generated in situ on Earth. Prior work that has shown that the matrix of igneous minerals is a medium in which progenitors of organic molecules assemble from H2O, C02 and N2 incorporated as minority "impurities" in minerals of igneous rocks during crystallization from H2O/CO2/N2-laden magmas. The underlying processes involve a redox. conversion whereby C, H, and N become chemically reduced, while 0 becomes oxidized to the peroxy state. During Year 02 the work will be divided into three tasks. Task 1: After carboxylic (fatty) acids and N-bearing compounds have been identified, other extractable organic molecules including lipids, oily substances and amino acids will be studied. Dedicated lipid analysis will be combined with gas chromatographic-mass spectroscopic (GCMS) analysis of organic compounds extracted from minerals and rocks. Task 2: Using infrared (IR) spectroscopy, C-H entities that are indicators for the organic progenitors in mineral matrices will be studied. A preliminary heating experiment with MgO single crystals has shown that the C-H entities can be pyrolyzed, causing the IR bands to disappear, but at room temperature the IR bands reappear in a matter of days to weeks. This work will be expanded, both by studying synthetic MgO crystals and olivine crystals from the Earth's upper mantle. The C-H bands will be compared to the published "organic" IR feature of dust in the interstellar medium (ISM) and interplanetary dust particles (IDP). Task 3: A paradox marks the evolution of early Life: Oxygen is highly toxic to primitive life, yet early organisms "learned" to detoxify reactive oxygen species, to utilize oxygen, and even produce it. Why would organisms on the early anaerobic Earth be under evolutionary pressure to evolve defenses against reactive oxygen species? Minerals in igneous rocks are now known to contain peroxy. When such minerals weather, the peroxy hydrolyzes to H2O2. The hypothesis will be tested whether organisms living in intimate contact with rock surfaces are subjected to a constant trickle of H202 and thus under stress to develop strategies to either detoxify the reactive oxygen species or repair the molecular damage that they cause. Understanding these processes is central to the Astrobiology mission. It opens new avenues toward understanding the evolution of early life on Earth, and the potential for aerobic life elsewhere. This Cooperative Agreement also has a strong educational and public outreach component involving high school, undergraduate students, and high school teachers.

Freund, Friedemann↗
NASA NTRS2005

TEM and NanoSIMS Study of Hydrated/Anhydrous Phase Mixed IDPs: Cometary or Asteroidal Origin?

Chondritic interplanetary dust particles (IDPs) are subdivided into (1) particles that form highly porous aggregates (chondritic porous "CP" IDPs), and (2) smooth particles ("CS" IDPs). Infrared (IR) spectroscopy has been a valuable tool for non-destructively determining the bulk mineralogy of IDPs. Most IDPs fall within three distinct IR groups: (1) olivine-rich particles, (2) pyroxene-rich particles, and (3) phyllosilicate-rich particles. From the IR studies, IDPs dominated by anhydrous minerals tend to be fine grained (CP), while phyllosilicate-rich IDPs are mostly CS. CP IDPs have been linked to cometary sources based on their compositions, spectral properties, and atmospheric entry velocities. Since no spectral signatures of hydrated minerals have been detected in comets, CS IDPs are thought to derive from primitive asteroids. Transmission electron microscopy (TEM) studies have revealed that the mineralogical distinctions between CP and CS IDPs are not always clear. Previous investigators have reported trace amounts of hydrous minerals in dominantly anhydrous particles. A better understanding of these particles will help to elucidate whether there is a genetic relationship between anhydrous and hydrated IDPs, provide insight into the earliest stages of aqueous alteration of primitive materials, and may help to determine whether comets have experienced any aqueous processing. Here we report a combined TEM and isotopic imaging study of an unusual anhydrous IDP with hydrated phases. Additional information is included in the original extended abstract.

Nakamura, K.↗
NASA NTRS2006

Comet Mineralogy as Inferred from Infrared Spectra of Comets

For most comets, infrared (IR) spectroscopy (remote sensing) is the method through which we diagnose the mineralogy and size distribution of dust in their comae. The shape and contrast of the IR spectral features depend on the particle size: optically active minerals (absorbing of visible and near-IR solar photons) and submicron solid grains or highly porous (> 90% vacuum) grains primarily contribute to the shapes of the observed resonances. Comet mineralogies typically are determined by fitting thermal emission models of ensembles of discrete mineral grains to observed IR spectral energy distributions. The absorptivities (Q-abs) and scattering efficiencies (Q-scat) of the discrete mineral grains are computed using Mie scattering, Maxwell-Garnet mixing, Discrete Dipole Approximation, and Multi-Layered Sphere codes. These techniques when applied to crystalline minerals, specifically olivine (Mg_x, Fe_1-x)2 Si04, x>0.9, require the use of ellipsoidal shaped particles with elongated axial ratios or hollow spheres to produce the shapes of the resonances observed both from comet comae and laboratory samples. The wavelength positions of the distinct resonances from submicron-radii crystalline silicates, as well as their thermal equilibrium temperatures, constrain the crystalline olivine to have a relatively high Mg-content (x>0.9, or Fo>90). Only resonances computed for submicron Mg-rich crystalline olivine and crystalline orthopyroxene match the observed IR spectral features. However, this has led to the interpretation that micron-radii and larger crystals are absent from comet comae. Furthermore, the mass fraction of silicate crystals is dependent upon whether just the submicron portion of the size distribution is being compared or the submicron crystals compare to the aggregates of porous amorphous silicates that are computationally tractable as porous spheres. We will discuss the Deep Impact results as examples of these challenges to interpreting mid-IR spectra of short-period comets.

Wooden, Diane H.↗
NASA NTRS2014

Laboratory Investigations of the Complex Refractory Organic Material Produced from Irradiation of Pluto Ice Analogs

Much of Pluto's surface consists of N2 ice with smaller amounts of CH4 and CO ices. Despite the low temperature (approximately 45K), chemistry can be driven in the surface ices by radiation processing such as cosmic ray bombardment. When cosmic rays strike the surface, much of their energy is dispersed in the form of secondary electrons, which in turn drive much of the resulting chemical reactions. Laboratory experiments designed to simulate the conditions on these icy bodies may provide insight into this chemistry. Significant progress has been made in the laboratory toward understanding the smaller, simple compounds produced in the solid phase by radiation processing of (N2, CH4, CO) ices (Bohn et al. 1994; Moore & Hudson 2003; Hodyss et al. 2011; Kim and Kaiser 2012). Recently Materese et al. (2014) used a variety of techniques to better characterize the refractory materials produced from the UV photo-irradiation of N2:CH4:CO ices. However, because Pluto's atmosphere is optically thick to Lyman-alpha UV radiation it is important to re-examine the results using an alternate radiation source. Our latest work has consisted of the analysis of refractory materials produced from the electron bombardment of low temperature N2(‐), CH4(‐), and CO(‐)containing ices (100:1:1). The ice mixture was chosen to be analogous to the known surface ices on Pluto and the radiation source was chosen to mimic the secondary electrons produced by cosmic rays bombardment. The residues were studied using multiple chemical techniques including, infrared (IR) spectroscopy, X‐ray absorption near‐edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC‐MS). The organic residues produced in these experiments can be seen as an analog for the refractory component of the surface of Pluto, and are compared with the residues previously obtained from UV photo‐irradiation. UV and near‐ IR spectroscopy of the surfaces of Pluto and Charon during the encounter with NASA's New Horizons spacecraft in 2015, will give the first close‐up measurements of ices and their photoproducts. Laboratory measurements and experiments will provide a better context for the data returned by the spacecraft.

organics↗
NASA NTRS2017

Ground-Based Detection of Deuterated Water in Comet C/2014 Q2 (Lovejoy) at IR Wavelengths

We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H2O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H2O and HDO, yielding production rates of 5.9 +/- 0.13 × 10(exp 29) and 3.6 +/- 1.0 × 10(exp 26) molecules/sec, respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water of 3.02 +/- 0.87 × 10(exp −4), i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 +/- 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 +/- 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H2O.

Paganini, L.↗
NASA NTRS2020

Reduced Dependence on Redundant Fasteners in Secondary-Bonded Composite Structures Using Modified Epoxy Matrix Resins

This report describes a sub-set of over 20 experiments conducted to optimize materials and processes to maximize mechanical properties of the assembled joint. Infrared (IR) spectroscopy was used to measure the chemical state of the ER surface after primary cure. Laminates were fabricated with various HR and ER layer thicknesses, inspected using ultrasonic testing, and mechanically tested to measure fracture toughness.

Frank L Palmieri↗
NASA NTRS2015

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.

Infrared Spectroscopy↗
NASA NTRS2001

Detection of Soluble and Fixed NH4+ in Clay Minerals by DTA and IR Reflectance Spectroscopy : A Potential Tool for Planetary Surface Exploration

Nitrogen is an essential element for life. It is the only element among the six major biogenic elements, C, O, S, O, P, H, whose presence in the Martian soil has not been positively and directly established. We describe here a study assessing the ability to detect NH4 in soils by two methods: differential thermal analysis (DTA) and infrared (IR) reflectance spectroscopy. Four standard clay minerals (kaolinite, montmorillonite, illite and attapulgite) and an altered tephra sample from Mauna Kea were treated with NH4 in this study. Samples of the NH4-treated and leached clays were analyzed by DTA and infrared (IR) reflectance spectroscopy to quantify the delectability of soluble and sorbed/fixed NH4. An exotherm at 270-280 C was clearly detected in the DTA curves of NH4-treated (non-leached) samples. This feature is assigned to the thermal decomposition reaction of NH4. Spectral bands observed at 1.56, 2.05, 2.12, 3.06, 3.3, 3.5, 5.7 and 7.0 microns in the reflectance spectra of NH4-treated and leached samples are assigned to the sorbed/fixed ammonium in the clays. The montmorillonite has shown the most intense absorbance due to fixed ammonium among the leached samples in this study, as a result of its high cation sorption capacity. It is concluded that the presence of sorbed or fixed NH4 in clays may be detected by infrared (IR) reflectance or emission spectroscopy. Distinction between soluble and sorbed NH4 may be achieved through the presence or absence of several spectral features assigned to the sorbed NH4 moietyi and, specifically, by use of the 4.2 micrometer feature assigned to solution NH4. Thermal analyses furnish supporting evidence of ammonia in our study through detection of N released at temperatures of 270-330 C. Based on these results it is estimated that IR spectra measured from a rover should be able to detect ammonia if present above 20 mg NH4/g sample in the surface layers. Orbital IR spectra and thermal analyses measured on a rover may be able to detect ammonia in soils as well but at higher abundances. The spectral features at 3.06 and 7.0 microns due to bound NH4 in clays and altered Hawaiian tephra appear to be the most promising for detection by orbital spectrometers. If N species are present on Mars the sedimentary deposits may be the best regions to look for them.

Janice, Bishop↗
NASA NTRS1998

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

Non-NASA Center↗
NASA NTRS2009

Spitzer IRS (8-30 micron) Spectra of Basaltic Asteroids 1459 Magnya and 956 Elisa: Mineralogy and Thermal Properties

We report preliminary results from Spitzer IRS (Infrared Spectrograph) spectroscopy of 956 Elisa, 1459 Magnya, and other small basaltic asteroids with the Spitzer IRS. Program targets include members of the dynamical family of the unique large differentiated asteroid 4 Vesta ("Vestoids"), several outer-main-belt basaltic asteroids whose orbits exclude them from originating on 4 Vesta, and the basaltic near-Earth asteroid 4055 Magellan. The preliminary thermal model (STM) fit to the 5--35 micron spectrum of 956 Elisa gives a radius of 5.4 +/- 0.3 km and a subsolar- point temperature of 282.2 +/- 0.5 K. This temperature corresponds to eta approximately equals 1.06 +/- 0.02, which is substantially higher than the eta approximately equals 0.756 characteristic of large main-belt asteroids. Unlike 4 Vesta and other large asteroids, therefore, 956 Elisa has significant thermal inertia in its surface layer. The wavelength of the Christiansen feature (emissivity maximum near 9 micron), the positions and shapes of the narrow maxima (10 micron, 11 micron) within the broad 9--14 micron silicate band, and the 19--20 micron minimum are consistent with features found in the laboratory spectra of diogenites and of low-Ca pyroxenes of similar composition (Wo<5, En50-En75).

Lim, Lucy F.↗
NASA NTRS1993

Composition of the Martian aerosols through near-IR spectroscopy

Near-infrared spectroscopy is a powerful technique to study the composition of planetary surfaces, as the main minerals exhibit absorption bands in this spectral range. It gave important information on the mineralogy and petrology of Mars in the past twenty years although in this case it is well known that a large fraction of light is scattered by the airborne particles before reaching the surface. The measured signal is thus the sum of two different contributions that should be studied separately: One from the surface and one from the aerosols that depends on their density, size distribution and composition. Data from the ISM imaging spectrometer are used here to derive the aerosols spectrum. They consist in sets of spectra (from 0.76 to 3.16 microns) of approximately 3000 pixels approximately 25x25 sq km in size. The resulting spectrum exhibits both water-ice and clay mineral features superimposed on a scattering continuum.

Erard, Stephane↗
NASA NTRS1996

Hot Carrier Dynamics in the X Valley in Si and Ge Measured by Pump-IR-Probe Absorption Spectroscopy

Si is the semiconductor of choice for nanoelectronic roadmap into the next century for computer and other nanodevices. With growing interest in Si, Ge, and Si(sub m)Ge(sub n) strained superlattices, knowledge of the carrier relaxation processes in these materials and structures has become increasingly important. The limited time resolution for earlier studies of carrier dynamics in Ge and Si, performed using Nd:glass lasers, was not sufficient to observe the fast cooling processes. In this paper, we present a direct measurement of hot carrier dynamics in the satellite X valley in Si and Ge by time-resolved infrared(IR) absorption spectroscopy, and show the potential of our technique to identify whether the X valley is the lowest conduction valley in semiconductor materials and structures.

Wang, W. B.↗
NASA NTRS1990

Comparison of P/Brorsen-Metcalf and P/Halley in the thermal infrared

Of the periodic comets, only comets Halley and Brorsen-Metcalf have periods of the order of 75 years and are bright enough to study spectroscopically in the infrared. Thermal IR spectroscopy of comet P/Brorsen-Metcalf near perihelion are presented and the results are compared to comet P/Halley.

Lynch, David K.↗
NASA NTRS2002

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR studies (telescopic and laboratory) have demonstrated that much of the carbon in the interstellar medium (ISM) is in complex organic species of a variety of types, but the distribution, abundance, and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEAST mission concept designed to conduct IR spectroscopic observations to detect and identify these materials to address outstanding important problems in astrobiology, astrochemistry, and astrophysics. Systematic studies include the observation of planetary nebulae and stellar outflows, protostellar objects, Solar System Objects, and galaxies, and multiple lines of sight through dense molecular clouds and the diffuse ISM. ABE will also search for evidence of D enrichment in complex molecules in all these environments. The mission is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cryogenic cross-dispersed spectrographs that share a single common slit. The 3 spectrometers each measure single spectral octaves (2.5-5, 5-10, 10-20 microns) and together cover the entire 2.5 - 20 micron region simultaneously. The spectrometers use state-of-the-art 1024x1024 pixel detectors, with a single InSb array for the 2.5-5 micron region and two Si:As arrays for the 5-10 and 10-20 micron regions. The spectral resolution is wavelength dependent but is greater than 2000 across the entire spectral range. ABE would operate in a heliocentric, Earth drift-away orbit and is designed to take maximum advantage of this environment for cooling, thermal stability, and mission lifetime. ABE would have a core science mission lasting approximately 1.5 years.

Sandford, Scott A.↗
NASA NTRS2002

The AstroBiology Explorer (ABE) MIDEX Mission Concept: Using Infrared Spectroscopy to Identify Organic Molecules in Space

One of the principal means by which organic compounds are detected and identified in space is by infrared spectroscopy. Past IR telescopic and laboratory studies have shown that much of the carbon in the interstellar medium (ISM) is in complex organic species but the distribution, abundance and evolutionary relationships of these materials are not well understood. The Astrobiology Explorer (ABE) is a MIDEX mission concept designed to conduct IR spectroscopic observations to detect and identify these materials and address outstanding problems in astrobiology, astrochemistry, and astrophysics. ABE's core science program includes observations of planetary nebulae and stellar outflows, protostellar objects, Solar System objects, and galaxies, and lines of sight through dense molecular clouds and the diffuse ISM. ABE is a cryogenically-cooled 60 cm diameter space telescope equipped with 3 cross-dispersed R-2000 spectrometers that share a single common slit. Each spectrometer measures one spectral octave and together cover the entire 2.5-20 micron region simultaneously. The spectrometers use state-of-the-art InSb and Si:As 1024x1024 pixel detectors. ABE would operate in a heliocentric, Earth drift-away orbit and have a core science mission lasting approximately 1.5 years. ABE is currently under study at NASA's Ames Research Center in collaboration with Ball Aerospace and Technologies Corp.

Sandford, Scott A.↗
NASA NTRSDate not supplied

Mineral composition of Al-rich float rocks in Jezero crater as seen by Super-Cam

During its traverse across the Jezero crater floor and western fan, the Perseverance rover encountered > 4000 float rocks – of variable size (up to ~ 50 cm) scattered on the ground without apparent connection to the surrounding stratigraphy [1]. Analysis performed using the SuperCam instrument’s [2,3,4], Laser Induced Breakdown Spectroscopy (LIBS) revealed a high concentration of Al 2 O 3 , Cr, Ti and Ni [5], and very low of Fe, Mg, Ca and Na [5, 1]. SuperCam’s infrared reflectance spectroscopy (IRS, between 1.3 and 2.6 μm) showed the presence of Al-rich aqueous alteration minerals (characteristic absorption bands of kaolinite and Al-smectites at 1.4 and 2.2 μm) as well as some (likely Cr-) spinels, identified uthrough their broad asymmetric 2 μm band, responsible for the concavity of IR spectra. These mineral species alone do not fully account for the spectral shapes; hence, the objective is to further investigate spectral modeling to determine the most probable mineral assemblages. Here, we present the results of modeling 17 light-toned float rocks, up to Sol 924, complementary to [1].

C. Royer↗
NASA NTRS1991

Absolute wind velocities in the lower thermosphere of Venus using infrared heterodyne spectroscopy

NASA's IR Telescope Facility and the McMath Solar Telescope have yielded absolute wind velocities in the Venus thermosphere for December 1985 to March 1987 with sufficient spatial resolution for circulation model discrimination. A qualitative analysis of beam-integrated winds indicates subsolar-to-antisolar circulation in the lower thermosphere; horizontal wind velocity was derived from a two-parameter model wind field of subsolar-antisolar and zonal components. A unique model fit common to all observing periods possessed 120 m/sec subsolar-antisolar and 25 m/sec zonal retrograde components, consistent with the Bougher et al. (1986, 1988) hydrodynamical models for 110 km.

Goldstein, Jeffrey J.↗