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NASA NTRS2024

Application of Long-Path Gas Cell Assisted Infrared Spectroscopy for Detection of Lunar Volatiles and Advanced Curation Efforts

The motivation behind analyzing gaseous samples from the Permanently Shadowed Regions (PSRs) on the lunar surface is built upon the volatiles observed during the LCROSS mission. Advanced curation techniques under cold conditions are essential to the critical scientific analysis of these returned samples. The detection of various volatiles in returned samples by gas-phase infrared (IR) spectroscopy is known to be a powerful tool to understand the resources present in planetary bodies and Astro-materials. The identification and quantification of volatile compounds in returned planetary samples and regolith simulants by advanced and custom-built analytical devices are areas of primary research interest in our group and the Planetary Exploration & Astromaterials Research Laboratory (PEARL) facility. In this context, we discuss recent advancements and experimental results for quick analysis of the major volatiles detected by the LCROSS (water, CO 2 , CH 3 OH, and NH 3 ) by a long-path gas cell/FTIR (Fourier Transform Infrared) spectrometer system. The applicability of this system is demonstrated by qualitative analysis of a series of volatiles measured individually. In addition, the linear dependence of absorption intensity on headspace sample volumes was checked by measuring gas-phase IR absorption spectra of increasing volumes of pure CO 2 gas aliquots. Finally, the instrument performance was evaluated by measuring the relative concentration of NH 3 (g) in methanol solution.

Curation↗
NASA NTRS2022

Identifying Shocked Feldspar on Mars Using Perseverance Spectroscopic Instruments: Implications for Geochronology Studies on Returned Samples

The Perseverance rover (Mars 2020) mission, the first step in NASA’s Mars Sample Return (MSR) program, will select samples for caching based on their potential to improve understanding Mars’ astrobiological, geological, geochemical, and climatic evolution. Geochronologic analyses will be among the key measurements planned for returned samples. Assessing a sample’s shock history will be critical because shock metamorphism could influence apparent sample age. Shock effects in one Mars-relevant mineral class, plagioclase feldspar, have been well- documented using various spectroscopy techniques (thermal infrared reflectance, emission, and transmission spectroscopy, Raman, and luminescence). A subset of these data will be obtained with the SuperCam and SHERLOC (Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals) instruments onboard Perseverance to inform caching decisions for MSR. Here, we review shock indicators in plagioclase feldspar as revealed in Raman, luminescence, and IR spectroscopy lab data, with an emphasis on Raman spectroscopy. We consider how this information may inform caching decisions for selecting optimal samples for geochronology measurements. We then identify challenges and make recommendations for both in situ measurements performed with SuperCam and SHERLOC and for supporting lab studies to enhance the success of geochronologic analyses after return to Earth.

mars↗
NASA NTRS1995

RY Scuti: Infrared and radio observations of the mass-loss wind of a massive binary star system

We report infrared (IR) imaging, IR photometry, IR spectroscopy, optical/IR photopolarimetry, and Very Large Array (VLA) radio observations of the peculiar binary star RY Scuti. These observations provide an unprecedented view of the detailed spatial structure of the equatorial mass-loss wind of a massive, luminous, 'overcontact' binary system. The binary star (0.43 AU separation) is surrounded by a flattened equatorial disk with an outer radius of approximately = 3 x 10(exp 16) cm (2000 AU) that emits strongly in the IR and radio. The inside of the disk is ionized and emits free-free radiation from hydrogen and 12.8 micrometers forbidden-line emission from (Ne II); the outside of the disk emits thermal radiation from silicate dust. Radio continuum emission is also produced in a compact H II region surrounding the binary. The dust may have a polycyclic aromatic hydrocarbon (PAH) component. We use a rudimentary geometric model in which the thermal IR and radio emission from the disk are assumed to arise in a pair of concentric toroidal rings to estimate the physical properties of the disk. The mean radius of the ionized gas toroid is approximately = 1.3 x 10(exp 16) cm (870 AU), and the mean radius of the dust toroid is approximately = 2.2 x 10(exp 16) cm (1470 AU). RY Scuti has a small intrinsic polarization, with the electric vector perpendicular to the equatorial disk, that is probably caused by electron scattering from hot gas close to the central binary. We conclude that neon in the nebula is overabundant with respect to hydrogen and helium by a factor of between 1.6 and 10. Our IR/radio image data suggest that the circumstellar disk is part of an extensive radiation driven mass-loss outflow that is strongly confined to the equatorial plane of the binary system. The sharp spatial separation of the outer dust torous from the inner ionized gas torus confirms earlier suggestions that dust formation in the circumstellar ejecta of very hot stars must occur in regions that are shielded from the hard radiation field.

Gehrz, R. D.↗
NASA NTRS1981

Low-energy electron effects on tensile modulus and infrared transmission properties of a polypyromellitimide film

Infrared (IR) spectroscopy and tensile modulus testing were used to evaluate the importance of experimental procedure on changes in properties of pyromellitic dianhydride-p,p prime-oxydianiline film exposed to electron radiation. The radiation exposures were accelerated, approximate equivalents to the total dose expected for a 30 year mission in geosynchronous Earth orbit. The change in the tensile modulus depends more on the dose rate and the time interval between exposure and testing than on total dose. The IR data vary with both total dose and dose rate. A threshold dose rate exists below which reversible radiation effects on the IR spectra occur. Above the threshold dose rate, irreversible effects occur with the appearance of a new band. Post-irradiation and in situ IR absorption bands are significantly different. It is suggested that the electron radiation induced metastable, excites molecular states.

Ferl, J. E.↗
NASA NTRS2004

Infrared Spectroscopy of Star Formation in Galactic and Extragalactic Regions

Last year we submitted and had accepted a paper entitled "The Far-Infrared Emission Line and Continuum Spectrum of the Seyfert Galaxy NGC 1068," by Spinoglio, L., Malkan, M., Smith. HA, Gonzalez-Alfonso, E., and Fischer, J. This analysis was based on the SWAS Monte Carlo code modeling of the OH lines in galaxies observed by ISO. Since that meeting last spring considerable effort has been put into improving the Monte Carlo code. A group of European astronomers, including Prof. Eduardo Gonzalez-Alfonso, had been performing Monte Carlo modeling of other molecules seen in ISO galaxies. We used portions of this grant to bring Prof. Gonzalez-Alfonso to Cambridge for an intensive working visit. A second major paper on the ISO IR spectroscopy of galaxies, "The Far Infrared Spectrum of Arp 220," Gonzalez-Alfonso, E., Smith. H., Fischer, J., and Cernicharo, J., is in press. Spitzer science development was the major component of this past year;s research. This program supported the development of five Early Release Objects for Spitzer observations on which Dr. Smith was Principal Investigator or Co-Investigator, and another five proposals for GO time. The early release program is designed to rapidly present to the public and the scientific community some exciting results from Spitzer in the first months of its operation. The Spitzer instrument and science teams submitted proposals for ERO objects, and a competitive selection process narrowed these down to a small group with exciting science and realistic observational parameters. This grant supported Dr. Smith's participation in the ERO process, including developing science goals, identifying key objects for observation, and developing the detailed AOR (observing formulae) to be use by the instruments for mapping, integrating, etc.). During this year Dr. Smith worked on writing up and publishing these early results. The attached bibliography includes six of Dr. Smith's articles. During this past year Dr. Smith also led or helped to develop proposals for ten Spitzer GO Programs, and three others. Appendix B lists the programs involved.

Smith, Howard A.↗
NASA NTRS1992

Infrared line diagnostics of active galactic nuclei

The CLOUDY photoionization code of Ferland (1991) is employed to predict intensities and ratios of the near-, mid-, and far-IR ionic fine-structure lines from AGN of the LINER and Seyfert types, and starbursts. The depths of varying the important model parameters, including ionization parameter, density, and optical depth, are investigated. The way in which detailed IR spectroscopy can reveal the presence of density inhomogeneities and abundance anomalies is shown, and the slope of the ionizing continuum and the amount of reddening and the reddening law are determined. The predictions of the present model and others are compared to the observed line ratios of the starburst galaxy M82 and of the Galactic center. No single-zone model adequately predicted all of the observed lines, but a simple combination of a starburst plus photodissociation region of higher density have a good fit for M82. The present model predictions are used to estimate the detectability of IR fine-structure lines in various active galaxies.

Spinoglio, Luigi↗
NASA NTRS1995

The spectral energy distribution of the z=3 quasar: HS 1946+7658

For the bright z = 3.02 radio-quiet quasar, HS 1946+7658, we have obtained radio to X-ray data within the past year: 5 GHz and 1415 MHz data from the Very Large Array (VLA); IR photometry at J, H, K, L prime (3.4 micrometers and N; IR spectroscopy; UBVRI photometry; optical spectrophotometry and high-resolution spectra; and an X-ray spectrum from the ROSAT Position Sensitive Proportional Counter (PSPC). The spectral energy distribution (SED) constructed from these data is compared to the mean SED for a set of low-redshift quasars, and while they appear generally similar, there are several differences. In relation to the low-redshift mean, the SED of HS 1946+7658 shows (1) only an upper limit at 10 micrometers (a rest wavelength of 2.5 micrometers, indicating that HS 1946+7658 does not have a strong near-IR excess such as hot dust would produce; (2) relatively weak Fe II and Balmer continuum emission at approximately 3000 A; and (3) a steeper turndown shortward of Ly alpha, even after correction for the Ly alpha forest absorption lines.

Kuhn, O.↗
NASA NTRS2012

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗
NASA NTRS1982

Radiation-induced loss of unsaturation in 1,2-polybutadiene

The radiation induced loss of unsaturation and methyl production in 1,2-polybutadiene (VB) was studied using IR spectroscopy. It was found that G(-1,2), which depends on the initial vinyl content, decreased from approximately 550 for VB with 98.5% 1,2 initially, to approximately 270 for VB with 85% 1,2 initially. G(-trans-1,4) ranged from approximately 21 for VB with 14% trans-1,4 to nearly zero for VB with less than 1% trans-1,4 initially. Methyl production was found to equal one methyl group formed for every 4-5 vinyl units consumed in the radiation-cyclized VB, in contrast to one methyl formed for every two vinyls reacted during cationic cyclization to give monocyclic structures. The IR spectra of gamma-irradiated VB were very similar to the spectra of UV-irradiated or thermally-treated VB at the same residual vinyl contents. It is suggested that the radiation-induced cyclization of VB occurs by a nonionic, nonradical 'energy chain' mechanism, which apparently holds for the cyclization of VB, whether induced by gamma-rays, UV radiation, or heat.

Golub, M. A.↗
NASA NTRS2015

NEAs: Phase Angle Dependence of Asteroid Class and Diameter from Observational Studies

We will discuss the results of a planned observation campaign of Near Earth Asteroids (NEAs), 1999 CU3, 2002 GM2, 2002 FG7, and 3691 Bede with instruments on the United Kingdom Infrared Telescope (UKIRT) from 15-Mar-2015 to 28-April 2015 UT. We will study the phase-angle dependence of the reflectance and thermal emission spectra. Recent publications reveal that the assignment of the asteroid class from visible and near-IR spectroscopy can change with phase angle for NEAs with silicate-bearing minerals on their surfaces (S-class asteroids) (Thomas et al. 2014, Icarus 228, 217; Sanchez et al. 2012 Icarus 220, 36). Only three of the larger NEAs have been measured at a dozen phase angles and the trends are not all the same, so there is not yet enough information to create a phase-angle correction. Also, the phase angle effect is not characterized well for the thermal emission including determination of the albedo and the thermal emission. The few NEAs were selected for our study amongst many possible targets based on being able to observe them through a wide range of phase angles, ranging from less than about 10 degrees to greater than 45 degrees over the constrained date range. The orbits of NEAs often generate short observing windows at phase angles higher than 45 deg (i.e., whizzing by Earth and/or close to dawn or dusk). Ultimately, lowering the uncertainty of the translation of asteroid class to meteorite analog and of albedo and size determinations are amongst our science goals. On a few specific nights, we plan to observe the 0.75-2.5 micron spectra with IRTF+SpeX for comparison with UKIRT data including 5-20 micron with UKIRT+UIST/Michelle to determine as best as possible the albedos. To ensure correct phasing of spectroscopic data, we augment with TRAPPIST-telescope light curves and R-band guider image data. Our observations will contribute to understanding single epoch mid-IR and near-IR measurements to obtain albedo, size and IR beaming parameters (the outcomes of thermal models) and asteroid spectral class.

phase-angle↗
NASA NTRS2015

Fe and O EELS Studies of Ion Irradiated Murchison CM2 Carbonaceous Chondrite Matrix

Introduction: The physical and chemical response of hydrated carbonaceous chondrite materials to space weathering processes is poorly understood. Improving this understanding is a key part of establishing how regoliths on primitive carbonaceous asteroids respond to space weathering processes, knowledge that supports future sample return missions (Hayabusa 2 and OSIRISREx) that are targeting objects of this type. We previously reported on He+ irradiation of Murchison matrix and showed that the irradiation resulted in amorphization of the matrix phyllosilicates, loss of OH, and surface vesiculation. Here, we report electron energy-loss spectroscopy (EELS) measurements of the irradiated material with emphasis on the Fe and O speciation. Sample and Methods: A polished thin section of the Murchison CM2 carbonaceous chondrite was irradiated with 4 kilovolts He(+) (normal incidence) to a total dose of 1 x 10(exp 18) He(+) per square centimeter. We extracted thin sections from both irradiated and unirradiated regions in matrix using focused ion beam (FIB) techniques with electron beam deposition for the protective carbon strap to minimize surface damage artifacts from the FIB milling. The FIB sections were analyzed using a JEOL 2500SE scanning and transmission electron microscope (STEM) equipped with a Gatan Tridiem imaging filter. EELS spectra were collected from 50 nanometer diameter regions with an energy resolution of 0.7 electronvolts FWHM at the zero loss. EELS spectra were collected at low electron doses to minimize possible artifacts from electron-beam irradiation damage. Results and Discussion: Fe L (sub 2,3) EELS spectra from matrix phyllosilicates in CM chondrites show mixed Fe(2+)/Fe(3+) oxidation states with Fe(3+)/Sigma Fe approximately 0.5. Fe L(sub 2,3) spectra from the irradiated/ amorphized matrix phyllosilicates show higher Fe(2+)/Fe(3+) ratios compared to spectra obtained from pristine material at depths beyond the implantation/amorphization layer. We also obtained O Ka spectra from phyllosilicates in both regions of the sample. The O Ka spectra show a pre-edge feature at approximately 530.5 electronvolts that is related to O 2p states hybridized with Fe 3d states. The intensity ratio of the O Ka pre-edge peak relative to the main part of the O Ka edge (that results from transitions of O 1s to 2p states) is lower in the irradiated layer compared to the pristine material and may reflect the loss of O (as OH) as was observed by IR spectroscopy. Conclusions: In addition to amorphization and OH loss, EELS spectra of He(+) irradiated matrix phyllosilicates in Murchison show that some of the Fe(3+) is reduced to Fe(2+). Spectral deconvolution is underway to extract quantitative ratios from the EELS spectra.

Keller, L. P.↗
NASA NTRS1973

Spectral reflectance and emittance of particulate materials. I - Theory. II - Application and results

The sizes, shapes, and complex refractive indices of particles are calculated in a study of the IR spectral reflectance of a semiinfinite medium composed of irregular particles of different materials. Geometric optics techniques with corrections for additional absorption due to particle edges and asperities is used in scattering and absorption calculations for particles larger than the wavelength. A Lorentz-Lorenz model is used to derive the averaged complex index of the medium, assuming that its individual particles are ellipsoids. Experimental results obtained on a Michelson interferometer for the spectral emittance of particulate mineral materials are compared with theoretical results. Good agreement between the experimental and theoretical results suggests the applicability, in remote IR spectroscopy, of the theoretical concepts applied in this study.

Emslie, A. G.↗
NASA NTRS1976

Accelerated heat-aging studies on fluororubber in various media

Heat-aging studies were conducted on fluororubber (copolymers of vinylidene fluoride and perfluoropropylene) using N,N-dicinnamylidene-1,6-hexanediamine, a Schiff's base of 1,6-hexanediamine, and MgO as acid acceptor. The principal technique employed was chemical stress relaxation for determining network changes brought about in the heat-aged fluororubber. This technique was backed up by swelling measurements, gel permeation chromatography, and IR spectroscopy. Stress relaxation curves are plotted for a wide range of variation in parameters (time, crosslinking density, state of curing, temperature, intermittent and continuous relaxation).

Kalfayan, S. H.↗
NASA NTRS1977

Physical-chemical examination of the N2O3-SO3-H2O system

It was found that when (NO)HSO4 is added to absolute H2SO4, specific conductivity rises sharply, possibly due to an increase in mutual interionic effects and viscosity as the (NO)HSO4 concentration rises. The addition of SO3 to the solution yielded a precipitate; a combination of analysis, IR spectroscopy and X-ray diffraction techniques indicated that this precipitate was (NO)HS2O7.

Linstroem, C.↗
NASA NTRS1982

Synthesis and characteristics of poly/bisdichloromaleimides/

The characteristics of six bisdichloromaleimides with different aromatic structures are investigated. The compounds are prepared by reacting 2,3-dichloromaleic anhydride with 1,5-diaminonaphthaline; bis (m-aminophenyl)methylphosphine oxide; 2,5-bis (p-aminophenyl) 1,3,4-oxadiazole; 3,3-bis (p-aminophenyl)phthalide; 9,9-bis (p-aminophenyl) fluorene; 10,10-bis (p-aminophenyl)anthrone. Dynamic thermogravity is used to determine the effect of structural differences on the thermal characteristics of these compounds. These compounds are polymerized by nucleophilic displacement of chlorine with 9,9-bis (p-aminophenyl)fluorene. The polymers are then characterized by IR spectroscopy and reduced viscosity measurements. The anaerobic char yields of these polymers at 800 C are found to range from 55-60%. A complete loss of weight is observed between 600-650 C in the presence of air. In addition, the thermal cross-linking of these polymers is investigated.

Varma, I. K.↗
NASA NTRS1982

The galactic center; Proceedings of the Workshop, California Institute of Technology, Pasadena, CA, January 7, 8, 1982

Observations and theoretical models of the galactic center are discussed, together with future observational capabilities. Radio observations of the molecular gas clouds and continuum around Sgr A are reported, as are IR continuum observations of the central 30 arcmin of the galaxy. IR data at 150, 200, and 300 microns are also cited, together with balloon-borne near-IR observations of the galactic central bulge. The galactic center has been examined with IR spectroscopy to characterize the ionized gas, the B-alpha and Ne II lines, the O I and O III lines in Sgr A, and the 10 micron emissions. Gamma ray observations have indicated the presence of positron annihilation, and further studies have been made in the 0.3-1.0 MeV range. Models for the compact source at the galactic center have considered accreting black holes, an accretion disk featuring Compton scattering to emit the positron radiation, and a protostar in the center of Sgr A. The gas motions and the potential triaxiality of the galactic center are discussed, and future NASA, ESA, Franco-Soviet, and Japanese spacecraft for X ray and gamma ray detection and mapping are described.

Riegler, G. R.↗