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NASA NTRS1994

Negative birefringent polyimide films

A negative birefringent film, useful in liquid crystal displays, and a method for controlling the negative birefringence of a polyimide film is disclosed which allows the matching of an application to a targeted amount of birefringence by controlling the degree of in-plane orientation of the polyimide by the selection of functional groups within both the diamine and dianhydride segments of the polyimide which affect the polyimide backbone chain rigidity, linearity, and symmetry. The higher the rigidity, linearity and symmetry of the polyimide backbone, the larger the value of the negative birefringence of the polyimide film.

Harris, Frank W.↗
NASA NTRS2006

Flora: A Proposed Hyperspectral Mission

In early 2004, one of the authors (Stephen Ungar, NASA GSFC) presented a mission concept called "Spectrasat" at the AVIRIS Workshop in Pasadena, CA. This mission concept grew out of the lessons learned from the Earth Observing-One (EO-1) Hyperion Imaging Spectrometer and was structured to more effectively accomplish the types of studies conducted with Hyperion. The Spectrasat concept represented an evolution of the technologies and operation strategies employed on EO-I. The Spectrasat concept had been preceded by two community-based missions proposed by Susan Ustin, UC Davis and Robert Green, NASA JPL. As a result of community participation, starting at this AVIRIS Workshop, the Spectrasat proposal evolved into the Flora concept which now represents the combined visions of Gregory Asner (Carnegie Institute), Stephen Ungar, Robert Green and Robert Knox, NASA GSFC. Flora is a proposed imaging spectrometer mission, designed to address global carbon cycle science issues. This mission centers on measuring ecological disturbance for purposes of ascertaining changes in global carbon stocks and draws heavily on experience gained through AVIRIS airborne flights and Hyperion space born flights. The observing strategy exploits the improved ability of imaging spectrometers, as compared with multi-spectral observing systems, to identify vegetation functional groups, detect ecosystem response to disturbance and assess the related discovery. Flora will be placed in a sun synchronous orbit, with a 45 meter pixel size, a 90 km swath width and a 31 day repeat cycle. It covers the spectral range from 0.4 to 2.5 micrometers with a spectral sampling interval of 10 nm. These specifications meet the needs of the Flora science team under the leadership of Gregory Asner. Robert Green, has introduced a spectrometer design for Flora which is expected to have a SNR of 600: 1 in the VNIR and 450: 1 in the SWIR. The mission team at NASA GSFC is designing an Intelligent Payload Module (IPM) designed to effectively reduce the volume of data required to be transmitted down to the ground. This paper discusses mission science objectives, describes the mission concept and presents the current status of possible funding opportunities leading to realization of the mission.

Ungar, Stephen↗
NASA NTRS2009

Use of UV Sources for Detection and Identification of Explosives

Measurement of Raman and native fluorescence emission using ultraviolet (UV) sources (<400 nm) on targeted materials is suitable for both sensitive detection and accurate identification of explosive materials. When the UV emission data are analyzed using a combination of Principal Component Analysis (PCA) and cluster analysis, chemicals and biological samples can be differentiated based on the geometric arrangement of molecules, the number of repeating aromatic rings, associated functional groups (nitrogen, sulfur, hydroxyl, and methyl), microbial life cycles (spores vs. vegetative cells), and the number of conjugated bonds. Explosive materials can be separated from one another as well as from a range of possible background materials, which includes microbes, car doors, motor oil, and fingerprints on car doors, etc. Many explosives are comprised of similar atomic constituents found in potential background samples such as fingerprint oils/skin, motor oil, and soil. This technique is sensitive to chemical bonds between the elements that lead to the discriminating separability between backgrounds and explosive materials.

Hug, William↗
NASA NTRS2009

A Design Basis for Spacecraft Cabin Trace Contaminant Control

Successful trace chemical contamination control is one of the components necessary for achieving good cabin atmospheric quality. While employing seemingly simple process technologies, sizing the active contamination control equipment must employ a reliable design basis for the trace chemical load in the cabin atmosphere. A simplified design basis that draws on experience gained from the International Space Station program is presented. The trace chemical contamination control design load refines generation source magnitudes and includes key chemical functional groups representing both engineering and toxicology challenges.

Perry, Jay L.↗
NASA NTRS2009

Detecting Airborne Mercury by Use of Polymer/Carbon Films

Films made of certain polymer/carbon composites have been found to be potentially useful as sensing films for detecting airborne elemental mercury at concentrations on the order of tens of parts per billion or more. That is to say, when the polymer/carbon composite films are exposed to air containing mercury vapor, their electrical resistances decrease by measurable amounts. Because airborne mercury is a health hazard, it is desirable to detect it with great sensitivity, especially in enclosed environments in which there is a risk of a mercury leak from lamps or other equipment. The present effort to develop polymerbased mercury-vapor sensors complements the work reported in NASA Tech Briefs Detecting Airborne Mercury by Use of Palladium Chloride (NPO- 44955), Vol. 33, No. 7 (July 2009), page 48 and De tecting Airborne Mer cury by Use of Gold Nanowires (NPO-44787), Vol. 33, No. 7 (July 2009), page 49. Like those previously reported efforts, the present effort is motivated partly by a need to enable operation and/or regeneration of sensors under relatively mild conditions more specifically, at temperatures closer to room temperature than to the elevated temperatures (greater than 100 C ) needed for regeneration of sensors based on noble-metal films. The present polymer/carbon films are made from two polymers, denoted EYN1 and EYN2 (see Figure 1), both of which are derivatives of poly-4-vinyl pyridine with amine functional groups. Composites of these polymers with 10 to 15 weight percent of carbon were prepared and solution-deposited onto the JPL ElectronicNose sensor substrates for testing. Preliminary test results showed that the resulting sensor films gave measurable indications of airborne mercury at concentrations on the order of tens of parts per billion (ppb) or more. The operating temperature range for the sensing films was 28 to 40 C and that the sensor films regenerated spontaneously, without heating above operating temperature (see Figure 2).

Shevade, Abhijit↗
NASA NTRS2010

The Spatial Distribution and Mineralogical Association of Organics in the Tagish Lake and Bells Carbonaceous Chondrites

Chondritic meteorites represent some of the most primitive Solar System materials available for laboratory analysis. While the presence of simple organic molecules has been well documented in such materials [1], little is known about their spatial distribution and to what extent, if any, they exhibit specific mineralogical associations. This dichotomy arises since organic analysis typically involves solvent extraction as a preliminary step. To address these issues we have used two-step laser mass spectrometry (L 2MS) to map in situ the spatial distribution of aromatic and conjugated organics at the micron scale in freshly exposed surfaces of the Tagish Lake and Bells carbonaceous chondrites. Our specific goals are two-fold; firstly to investigate if and how abundance of organic species varies within the meteorite matrix both as an ensemble, and with respect to functional group (e.g., R-OH vs. RCH3) and between members of the same homologous series (e.g., R-H vs. R-(CH2)H). Secondly, to determine whether observed spatial variations can be related to specific mineralogical and/or physical characteristics of the host matrix. In regard to the latter we are particularly interested in the role that carbonaceous nanoglobules [2] play as reservoirs of organic matter. Such globules, which are believed to have formed by photochemical processing of organic-rich ices in the presolar cold molecular cloud or the outermost reaches of the early protosolar disk, are abundant in both the Bells and Tagish Lake chondrites and are noteworthy for having particularly high enrichments in 2H and 15N [3,4].

Clemett, S. J.↗
NASA NTRS2010

Silica/Polymer and Silica/Polymer/Fiber Composite Aerogels

Aerogels that consist, variously, of neat silica/polymer alloys and silica/polymer alloy matrices reinforced with fibers have been developed as materials for flexible thermal-insulation blankets. In comparison with prior aerogel blankets, these aerogel blankets are more durable and less dusty. These blankets are also better able to resist and recover from compression . an important advantage in that maintenance of thickness is essential to maintenance of high thermal-insulation performance. These blankets are especially suitable as core materials for vacuum- insulated panels and vacuum-insulated boxes of advanced, nearly seamless design. (Inasmuch as heat leakage at seams is much greater than heat leakage elsewhere through such structures, advanced designs for high insulation performance should provide for minimization of the sizes and numbers of seams.) A silica/polymer aerogel of the present type could be characterized, somewhat more precisely, as consisting of multiply bonded, linear polymer reinforcements within a silica aerogel matrix. Thus far, several different polymethacrylates (PMAs) have been incorporated into aerogel networks to increase resistance to crushing and to improve other mechanical properties while minimally affecting thermal conductivity and density. The polymethacrylate phases are strongly linked into the silica aerogel networks in these materials. Unlike in other organic/inorganic blended aerogels, the inorganic and organic phases are chemically bonded to each other, by both covalent and hydrogen bonds. In the process for making a silica/polymer alloy aerogel, the covalent bonds are introduced by prepolymerization of the methacrylate monomer with trimethoxysilylpropylmethacrylate, which serves as a phase cross-linker in that it contains both organic and inorganic monomer functional groups and hence acts as a connector between the organic and inorganic phases. Hydrogen bonds are formed between the silanol groups of the inorganic phase and the carboxyl groups of the organic phase. The polymerization process has been adapted to create interpenetrating PMA and silica-gel networks from monomers and prevent any phase separations that could otherwise be caused by an overgrowth of either phase. Typically, the resulting PMA/silica aerogel, without or with fiber reinforcement, has a density and a thermal conductivity similar to those of pure silica aerogels. However, the PMA enhances mechanical properties. Specifically, flexural strength at rupture is increased to 102 psi (=0.7 MPa), about 50 times the flexural strength of typical pure silica aerogels. Resistance to compression is also increased: Applied pressure of 17.5 psi (=0.12 MPa) was found to reduce the thicknesses of several composite PMA/silica aerogels by only about 10 percent.

Ou, Danny↗
NASA NTRS2010

Comparison of the Organic Composition of Cometary Samples with Residues Formed from the UV Irradiation of Astrophysical Ice Analogs

The NASA Stardust mission successfully collected material from Comet 81P/Wild 2 [1], including authentic cometary grains [2]. X-ray absorption near-edge structure (XANES) spectroscopy analysis of these samples indicates the presence of oxygen-rich and nitrogen-rich organic materials, which contain a broad variety of functional groups (carbonyls, C=C bonds, aliphatic chains, amines, arnides, etc.) [3]. One component of these organics appears to contain very little aromatic carbon and bears some similarity to the organic residues produced by the irradiation of ices of interstellar/cometary composition, Stardust samples were also recently shown to contain glycine, the smallest biological amino acid [4]. Organic residues produced froth the UV irradiation of astrophysical ice analogs are already known to contain a large suite of organic molecules including amino acids [5-7], amphiphilic compounds (fatty acids) [8], and other complex species. This work presents a comparison between XANES spectra measured from organic residues formed in the laboratory with similar data of cometary samples collected by the Stardust mission

Milam, S. N.↗
NASA NTRS2010

Functionalization of Single-Wall Carbon Nanotubes by Photo-Oxidation

new technique for carbon nanotube oxidation was developed based upon the photo-oxidation of organic compounds. The resulting method is more benign than conventional oxidation approaches and produces single-wall carbon nanotubes (SWCNTs) with higher levels of oxidation. In this procedure, an oxygen saturated suspension of SWNTs in a suitable solvent containing a singlet oxygen sensitizer, such as Rose Bengal, is irradiated with ultraviolet light. The resulting oxidized tubes are recovered by filtering the suspension, followed by washing to remove any adsorbed solvent and sensitizer, and drying in a vacuum oven. Chemical analysis by FT-infrared and x-ray photoelectron spectroscopy revealed that the oxygen content of the photo-oxidized SWCNT was 11.3 atomic % compared to 6.7 atomic % for SWCNT that had been oxidized by standard treatment in refluxing acid. The photo-oxidized SWCNT produced by this method can be used directly in various polymer matrixes, or can be further modified by chemical reactions at the oxygen functional groups and then used as additives. This method may also be suitable for use in oxidation of multiwall carbon nanotubes and graphenes.

Lebron-Colon, Marisabel↗
NASA NTRS2010

NASA-JSC Protocol for the Characterization of Single Wall Carbon Nanotube Material Quality

It is well known that the raw as well as purified single wall carbon nanotube (SWCNT) material always contain certain amount of impurities of varying composition (mostly metal catalyst and non-tubular carbon). Particular purification method also creates defects and/or functional groups in the SWCNT material and therefore affects the its dispersability in solvents (important to subsequent application development). A number of analytical characterization tools have been used successfully in the past years to assess various properties of nanotube materials, but lack of standards makes it difficult to compare these measurements across the board. In this work we report the protocol developed at NASA-JSC which standardizes measurements using TEM, SEM, TGA, Raman and UV-Vis-NIR absorption techniques. Numerical measures are established for parameters such as metal content, homogeneity, thermal stability and dispersability, to allow easy comparison of SWCNT materials. We will also report on the recent progress in quantitative measurement of non-tubular carbon impurities and a possible purity standard for SWCNT materials.

Arepalli, Sivaram↗
NASA NTRS2011

Correlated Microanalysis of Cometary Organic Grains Returned by Stardust

Preliminary examination (PE) of samples returned from Comet 81P/Wild 2 by the NASA Stardust mission revealed a wide variety of carbonaceous samples [e.g. 1]. Carbonaceous matter is present as inclusions, rinds, and films in polyminerallic terminal particles [2-4], as carbon-rich particles along track walls [2, 5, 6], and as organic matter in aerogel around tracks [7, 8]. The organic chemistry of these samples ranges from purely aliphatic hydrocarbons to highly-aromatic material, often modified by various organic functional groups [2, 4, 5, 9-11]. Difficulty arises when interpreting the genesis of these carbonaceous samples, since contaminants could be introduced from the spacecraft [12], aerogel [1, 8], or during sample preparation. In addition, hypervelocity capture into aerogel may have heated cometary material in excess of 1000 C, which could have significantly altered the structure and chemistry of carbonaceous matter. Fortunately, much of this contamination or alteration can be identified through correlated microanalysis with transmission electron microscopy (TEM), scanning-transmission X-ray microscopy (STXM), and nanoscale secondary ion mass spectroscopy (SIMS).

DeGregorio, B. T.↗
NASA NTRS2003

Enhanced Raman Microprobe Imaging of Single-Wall Carbon Nanotubes

We explore Raman microprobe capabilities to visualize single wall carbon nanotubes (SWCNTs). Although this technique is limited to a micron scale, we demonstrate that images of individual SWCNTs, bundles or their agglomerates can be generated by mapping Raman active elementary excitations. We measured the Raman response from carbon vibrations in SWCNTs excited by confocal scanning of a focused laser beam. Carbon vibrations reveal key characteristics of SWCNTs as nanotube diameter distribution (radial breathing modes, RBM, 100-300 cm(exp -1)), presence of defects and functional groups (D-mode, 1300-1350 cm(exp -1)), strain and oxidation states of SWCNTs, as well as metallic or semiconducting character of the tubes encoded in the lineshape of the G-modes at 1520-1600 cm(exp - 1). In addition, SWCNTs are highly anisotropic scatterers. The Raman response from a SWCNT is maximal for incident light polarization parallel to the tube axis and vanishing for perpendicular directions. We show that the SWCNT bundle shape or direction can be determined, with some limitations, from a set of Raman images taken at two orthogonal directions of the incident light polarization.

Hadjiev, V. G.↗
NASA NTRS2005

Modifying Silicates for Better Dispersion in Nanocomposites

An improved chemical modification has been developed to enhance the dispersion of layered silicate particles in the formulation of a polymer/silicate nanocomposite material. The modification involves, among other things, the co-exchange of an alkyl ammonium ion and a monoprotonated diamine with interlayer cations of the silicate. The net overall effects of the improved chemical modification are to improve processability of the nanocomposite and maximize the benefits of dispersing the silicate particles into the polymer. Some background discussion is necessary to give meaning to a description of this development. Polymer/silicate nanocomposites are also denoted polymer/clay composites because the silicate particles in them are typically derived from clay particles. Particles of clay comprise layers of silicate platelets separated by gaps called "galleries." The platelet thickness is 1 nm. The length varies from 30 nm to 1 m, depending on the silicate. In order to fully realize the benefits of polymer/silicate nanocomposites, it is necessary to ensure that the platelets become dispersed in the polymer matrices. Proper dispersion can impart physical and chemical properties that make nanocomposites attractive for a variety of applications. In order to achieve nanometer-level dispersion of a layered silicate into a polymer matrix, it is typically necessary to modify the interlayer silicate surfaces by attaching organic functional groups. This modification can be achieved easily by ion exchange between the interlayer metal cations found naturally in the silicate and protonated organic cations - typically protonated amines. Long-chain alkyl ammonium ions are commonly chosen as the ion-exchange materials because they effectively lower the surface energies of the silicates and ease the incorporation of organic monomers or polymers into the silicate galleries. This completes the background discussion. In the present improved modification of the interlayer silicate surfaces, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

Campbell, Sandi↗
NASA NTRS2005

Miniature Laboratory for Detecting Sparse Biomolecules

A miniature laboratory system has been proposed for use in the field to detect sparsely distributed biomolecules. By emphasizing concentration and sorting of specimens prior to detection, the underlying system concept would make it possible to attain high detection sensitivities without the need to develop ever more sensitive biosensors. The original purpose of the proposal is to aid the search for signs of life on a remote planet by enabling the detection of specimens as sparse as a few molecules or microbes in a large amount of soil, dust, rocks, water/ice, or other raw sample material. Some version of the system could prove useful on Earth for remote sensing of biological contamination, including agents of biological warfare. Processing in this system would begin with dissolution of the raw sample material in a sample-separation vessel. The solution in the vessel would contain floating microscopic magnetic beads coated with substances that could engage in chemical reactions with various target functional groups that are parts of target molecules. The chemical reactions would cause the targeted molecules to be captured on the surfaces of the beads. By use of a controlled magnetic field, the beads would be concentrated in a specified location in the vessel. Once the beads were thus concentrated, the rest of the solution would be discarded. This procedure would obviate the filtration steps and thereby also eliminate the filter-clogging difficulties of typical prior sample-concentration schemes. For ferrous dust/soil samples, the dissolution would be done first in a separate vessel before the solution is transferred to the microbead-containing vessel.

Lin, Ying↗
NASA NTRS2010

Ultraviolet Irradiation of Pyrimidine in Interstellar Ice Analogs: Formation and Photo-Stability of Nucleobases

Astrochemistry laboratory experiments recently showed that molecules of prebiotic interest can potentially form in space, as supported by the detection of amino acids in organic residues formed by the UV photolysis of ices simulating interstellar and cometary environments (H2O, CO, CO2, CH3OH, NH3, etc.). Although the presence of amino acids in the interstellar medium (ISM) is still under debate, experiments and the detection of amino acids in meteorites both support a scenario in which prebiotic molecules could be of extraterrestrial origin, before they are delivered to planets by comets, asteroids, and interplanetary dust particles. Nucleobases, the informational subunits of DNA and RNA, have also been detected in meteorites, although they have not yet been observed in the ISM. Thus, these molecules constitute another family of prebiotic compounds that can possibly form via abiotical processes in astrophysical environments. Nucleobases are nitrogen-bearing cyclic aromatic species with various functional groups attached, which are divided into two classes: pyrimidines (uracil, cytosine, and thymine) and purines (adenine and guanine). In this work, we study how UV irradiation affects pyrimidine mixed in interstellar ice analogs (H2O, NH3, CH3OH). In particular, we show that the UV irradiation of H2O:pyrimidine mixtures leads to the production of oxidized compounds including uracil, and show that both uracil and cytosine are formed upon irradiation of H2O:NH3:pyrimidine mixtures. We also study the photostability of pyrimidine and its photoproducts formed during these experiments.

Nuevo, Michel↗
NASA NTRS2012

Electrochemical Ultracapacitors Using Graphitic Nanostacks

Electrochemical ultracapacitors (ECs) have been developed using graphitic nanostacks as the electrode material. The advantages of this technology will be the reduction of device size due to superior power densities and relative powers compared to traditional activated carbon electrodes. External testing showed that these materials display reduced discharge response times compared to state-of-the-art materials. Such applications are advantageous for pulsed power applications such as burst communications (satellites, cell phones), electromechanical actuators, and battery load leveling in electric vehicles. These carbon nanostructures are highly conductive and offer an ordered mesopore network. These attributes will provide more complete electrolyte wetting, and faster release of stored charge compared to activated carbon. Electrochemical capacitor (EC) electrode materials were developed using commercially available nanomaterials and modifying them to exploit their energy storage properties. These materials would be an improvement over current ECs that employ activated carbon as the electrode material. Commercially available graphite nanofibers (GNFs) are used as precursor materials for the synthesis of graphitic nanostacks (GNSs). These materials offer much greater surface area than graphite flakes. Additionally, these materials offer a superior electrical conductivity and a greater average pore size compared to activated carbon electrodes. The state of the art in EC development uses activated carbon (AC) as the electrode material. AC has a high surface area, but its small average pore size inhibits electrolyte ingress/egress. Additionally, AC has a higher resistivity, which generates parasitic heating in high-power applications. This work focuses on fabricating EC from carbon that has a very different structure by increasing the surface area of the GNF by intercalation or exfoliation of the graphitic basal planes. Additionally, various functionalities to the GNS surface will be added that can exhibit pseudocapacitance. This pseudocapacitance exhibits faradaic (charge transfer) properties that can further increase the overall relative and volumetric capacitance of the material. A process is also proposed to use GNF as a precursor material to fabricate GNS that will be used as EC electrodes. This results in much better electrical conductivity than activated carbon. This is advantageous for high-pulsed-power applications to reduce parasitic heating. Larger average pore size allows more complete electrolyte wetting (faster charge transfer kinetics). These properties contribute to a lowered equivalent series resistance (ESR), increased specific power, shorter charging times, and decreased parasitic heating. The high density of basal plane edges provides nucleation sites for activation (addition of hydrophilic functional groups) that facilitate electrolyte wetting, and will contribute to pseudocapacitance.

Marotta, Christopher↗
NASA NTRS2011

Visible and Near-IR Reflectance Spectra of Smectite Acquired Under Dry Conditions for Interpretation of Martian Surface Mineralogy

Visible and near-IR (VNIR) spectra from the MEx OMEGA and the MRO CRISM hyper-spectral imaging instruments have spectral features associated with the H2O molecule and M OH functional groups (M = Mg, Fe, Al, and Si). Mineralogical assignments of martian spectral features are made on the basis of laboratory VNIR spectra, which were often acquired under ambient (humid) conditions. Smectites like nontronite, saponite, and montmorillionite have interlayer H2O that is exchangeable with their environment, and we have acquired smectite reflectance spectra under dry environmental conditions for interpretation of martian surface mineralogy. We also obtained chemical, Moessbauer (MB), powder X-ray diffraction (XRD), and thermogravimetric (TG) data to understand variations in spectral properties. VNIR spectra were recorded in humid lab air at 25-35C, in a dynamic dry N2 atmosphere (50-150 ppmv H2O) after exposing the smectite samples (5 nontronites, 3 montmorillionites, and 1 saponite) to that atmosphere for up to approximately l000 hr each at 25-35C, approximately 105C, and approximately 215C, and after re-exposure to humid lab air. Heating at 105C and 215C for approximately 1000 hr is taken as a surrogate for geologic time scales at lower temperatures. Upon exposure to dry N2, the position and intensity of spectral features associated with M-OH were relatively insensitive to the dry environment, and the spectral features associated with H2O (e.g., approximately 1.90 micrometers) decreased in intensity and are sometimes not detectable by the end of the 215C heating step. The position and intensity of H2O spectral features recovered upon re-exposure to lab air. XRD data show interlayer collapse for the nontronites and Namontmorillionites, with the interlayer remaining collapsed for the latter after re-exposure to lab air. The interlayer did not collapse for the saponite and Ca-montmorillionite. TG data show that the concentration of H2O derived from structural OH was invariant to the dry N2 treatment for saponite and the montmorillionites, but the nontronites had additional structural OH after treatment. Upon exposure to dry N2, the VNIR spectra also acquired a red slope with decreasing albedo between approximately 0.4 and approximately 2.0 micrometers. The magnitude of the effects covaries with exposure time to dry N2 and heating temperature. Upon re-exposure to lab air, the slope and albedo do not completely recover to pre-exposure values. MB data show that these effects do not result from partial reduction of ferric to ferrous iron, and TG data show they do not result from loss of structural OH. Possible explanations include formation of small clusters of (superparamagnetic) ferric oxide and reduced smectite crystallinity. The difference in spectral properties between spectra acquired in humid lab air and under dry conditions are consequential for interpretation of CRISM and OMEGA spectra. For example, nontronite by itself and not nontronite plus ferrihydrite can account for the red spectral slope in martian spectra where nontronite is indicated by the Fe-OH spectral features.

Morris, Richard V.↗
NASA NTRS2012

Isotopic Anomalies in Primitive Solar System Matter: Spin-State-Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and N-15. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula, Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and N-15 and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large N-15 enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, N-15 enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both N-15 and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest N=15 enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that solar system N-15 and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.

Wirstrom, Eva S.↗