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The Origins, Spectral Interpretation, Resource Identification, and Security–Regolith Explorer (OSIRIS-REx) spacecraft launched on September 8, 2016, beginning a seven-year journey to return at least 60 g of asteroid material from (101955) Bennu to Earth. During the outbound cruise, Doppler tracking of the spacecraft observed a small but measurable acceleration when the sample return capsule (SRC) was first placed in sunlight. Subsequent analysis determined that outgassing from the SRC is the most likely cause for the acceleration. This outgassing received combined engineering and scientific attention because it has potential implications both for spacecraft navigation performance and for contamination of the collected samples. Thermal modeling, laboratory studies of SRC materials, and monitoring of the acceleration are all consistent with H2O as the main component of the outgassing. Dedicated, in-flight campaigns continued to expose the SRC to sunlight until the acceleration dropped to the acceleration noise floor. Any residual amounts of H2O outgassing are not considered to be a hazard with regards to mission operations or pristine sample acquisition. The sample stow procedure has been updated to ensure that no direct line of site exists between any residual outgassing and the samples during future operations. Similar outgassing of the Stardust SRC probably also occurred. No adverse contamination of Stardust samples was observed that could be associated with this process. Future missions that use similar reentry vehicles should consider procedures to test for and, if necessary, mediate such outgassing after launch.

The CORSAIR (COmet Rendezvous, Sample Acquisition, Investigation, and Return) mission was a proposal for the NASA New Frontiers program. It belongs to the Comet Surface Sample Return mission theme which focuses on acquiring and returning to Earth a macroscopic sample from the surface of a comet nucleus. CORSAIR uses a harpoon-based Sample Acquisition System (SAS) with the spacecraft hovering several meters above the comet surface. This stand-off strategy overcomes disadvantages of other systems such as drills. Since comets are low gravity objects, those techniques would require anchoring before sampling, which is not necessary here. Moreover, the harpoon-based system allows for acquiring several samples from different locations on the comet maximizing the scientific output of the mission. Each SAS assembly consists of a pyro-driven launcher, a Sample Acquisition and Retrieval Projectile (SARP) and a retraction system using a deployable composite boom structure. In order to collect enough cometary material, the launcher has to provide the required kinetic energy to the SARP. Due to high energy densities, pyrotechnically actuated devices ultimately reduce the overall system mass and dimensions. First, the scientific and technological background of the CORSAIR mission is explained. Then, an overview of the development, design and testing of the launcher is given. Finally, the launcher theory is introduced explaining the entire reaction chain: initiation → gas dynamics → SARP motion.

We discuss in a thermodynamic, geologically empirical way the long-term nature of the stable majority ices that could be present in Kuiper Belt Object 2014 MU69 after its 4.6 Gyr residence in the EKB as a cold classical object. Considering the stability versus sublimation into vacuum for the suite of ices commonly found on comets, Centaurs, and KBOs at the average ~40K sunlit surface temperature of MU69 over Myr to Gyr, we find only 3 common ices that are truly refractory: HCN, CH3OH, and H2O (in order of increasing stability). NH3 and H2CO ices are marginally stable and may be removed by any positive temperature excursions in the EKB, as produced every 1e8 - 1e9 yrs by nearby supernovae and passing O/B stars. To date the NH team has reported the presence of abundant CH3OH and evidence for H2O on MU69s surface (Lisse et al. 2017, Grundy et al. 2020). NH3 has been searched for, but not found. We predict that future absorption feature detections will be due to an HCN or poly-H2CO based species. Consideration of the conditions present in the EKB region during the formation era of MU69 lead us to infer that it formed "in the dark", in an optically thick mid-plane, unable to see the nascent, variable, highly luminous Young Stellar Object-TTauri Sun, and that KBOs contain HCN and CH3OH ice phases in addition to the H2O ice phases found in their Short Period comet descendants. Finally, when we apply our ice thermal stability analysis to bodies/populations related to MU69, we find that methanol ice may be ubiquitous in the outer solar system; that if Pluto is not a fully differentiated body, then it must have gained its hypervolatile ices from proto-planetary disk sources in the first few Myr of the solar systems existence; and that hypervolatile rich, highly primordial comet C/2016 R2 was placed onto an Oort Cloud orbit on a similar timescale., Comment: 34 Pages, 5 Figures, 2 SOM Tables

Laboratory spectra have shown that CO2 is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer Solar System as well as dust grain surfaces in the interstellar medium (ISM). IR absorption band profiles of CO2 within ice mixtures containing H2O and CH3OH change with respect to temperature and mixture ratios. In this particular study, the CO2 asymmetric stretching mode near 4.3 m (2350 cm (exp-1)), overtone mode near 1.97 m (5080 cm (exp-1)), and the combination bands near 2.7 m (3700 cm (exp-1)), 2.8 m (3600 cm (exp-1)), and 2.02 m (4960 cm (exp -1)), are systematically observed in different mixtures with H2O and CH3OH in temperature ranges from 15K to 150 K. Additionally, some high-temperature deposits (T greater than 50 K) of H2O, CH3OH, and CO2 ice mixtures were performed. These data may then be used to interpret infrared observational data obtained from icy surfaces in the outer Solar System and beyond.

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

Several of the icy satellites of Saturn show the spectroscopic signature of the asymmetric stretching mode of C–O in carbon dioxide (CO2) at or near the nominal solid-phase laboratory wavelength of 4.2675 μm (2343.3 cm−1), discovered with the Visible-Infrared Mapping Spectrometer (VIMS) on the Cassini spacecraft. We report here on an analysis of the variation in wavelength and width of the CO2 absorption band in the spectra of Phoebe, Iapetus, Hyperion, and Dione. Comparisons are made to laboratory spectra of pure CO2, CO2 clathrates, ternary mixtures of CO2 with other volatiles, implanted and adsorbed CO2 in non-volatile materials, and ab initio theoretical calculations of CO2 * nH2O. At the wavelength resolution of VIMS, the CO2 on Phoebe is indistinguishable from pure CO2 ice (each molecule’s nearby neighbors are also CO2) or type II clathrate of CO2 in H2O. In contrast, the CO2 band on Iapetus, Hyperion, and Dione is shifted to shorter wavelengths (typically ∼4.255 μm (∼2350.2 cm−1)) and broadened. These wavelengths are characteristic of complexes of CO2 with different near-neighbor molecules that are encountered in other volatile mixtures such as with H2O and CH3OH, and non-volatile host materials like silicates, some clays, and zeolites. We suggest that Phoebe’s CO2 is native to the body as part of the initial inventory of condensates and now exposed on the surface, while CO2 on the other three satellites results at least in part from particle or UV irradiation of native H2O plus a source of C, implantation or accretion from external sources, or redistribution of native CO2 from the interior. The analysis presented here depends on an accurate VIMS wavelength scale. In preparation for this work, the baseline wavelength calibration for the Cassini VIMS was found to be distorted around 4.3 μm, apparently as a consequence of telluric CO2 gas absorption in the pre-launch calibration. The effect can be reproduced by convolving a sequence of model detector response profiles with a deep atmospheric CO2 absorption profile, producing distorted detector profile shapes and shifted central positions. In a laboratory blackbody spectrum used for radiance calibration, close examination of the CO2 absorption profile shows a similar deviation from that expected from a model. These modeled effects appear to be sufficient to explain the distortion in the existing wavelength calibration now in use. A modification to the wavelength calibration for 13 adjacent bands is provided. The affected channels span about 0.2 μm centered on 4.28 μm. The maximum wavelength change is about 10 nm toward longer wavelength. This adjustment has implications for interpretation of some of the spectral features observed in the affected wavelength interval, such as from CO2, as discussed in this paper.

Using new laboratory spectra, we have calculated the real and imaginary parts of the index of refraction of amorphous and crystalline H2O-ice from 20 to 150 K in the frequency range 9000–3800 cm−1 (1.1–2.6 μm) at a spectral resolution of 1 cm−1. These optical constants can be used to create model spectra for comparison to spectra from Solar System objects. We also analyzed the differences between the amorphous and crystalline H2O-ice spectra, including weakening of bands and shifting of bands to shorter wavelength in amorphous H2O-ice spectra. We have also observed two spectrally distinct phases of amorphous H2O-ice.

The AstroBiology Explorer (ABE) and the Astrobiology Space InfraRed Explorer (ASPIRE) Mission Concepts are two missions designed to address the questions (1) Where do we come from? and (2) Are we alone? as outlined in NASA s Origins Program using infrared spectroscopy to explore the identity, abundance, and distribution of molecules of astrobiological importance throughout the Universe. The ABE mission s observational program is focused on six tasks to: (1) Investigate the evolution of ice and organics in dense clouds and star formation regions, and the young stellar/planetary systems that form in them; (2) Measure the evolution of complex organic molecules in stellar outflows; (3) Study the organic composition of a wide variety of solar system objects including asteroids, comets, and the planets and their satellites; (4) Identify organic compounds in the diffuse interstellar medium and determine their distribution , abundance, and change with environment; (5) Detect and identify organic compounds in other galaxies and determine their dependence on galactic type; and (6) Measure deuterium enrichments in interstellar organics and use them as tracers of chemical processes. The ASPIRE mission s observational program expands upon ABE's core mission and adds tasks that (7) Address the role of silicates in interstellar organic chemistry; and (8) Use different resolution spectra to assess the relative roles and abundances of gas- and solid-state materials. ABE (ASPIRE) achieves these goals using a highly sensitive, cryogenically-cooled telescope in an Earth drift-away heliocentric orbit, armed with a suite of infrared spectrometers that cover the 2.5-20(40) micron spectral region at moderate spectral resolution (R>2000). ASPIRE's spectrometer complement also includes a high-resolution (R>25,000) module over the 4-8 micron spectral region. Both missions target lists are chosen to observe a statistically significant sample of a large number of objects of varied types in support of the tasks outline above. The ABE and ASPIRE mission lifetimes are designed to be 14 months and 3 years, respectively, both with significant cryogen and propellant lifetime margins to support an extended observing campaign. The ABE/ASPIRE mission concepts and their supporting Science Teams are led by Principal Investigator Dr. Scott Sandford of NASA s Ames Research Center, with industry partner Ball Aerospace Technologies Ltd., and managed by Jet Propulsion Laboratory. The ABE/ASPIRE Science Operations will be carried out at NASA s Ames Research Center, and the ABE/ASPIRE database will be archived at Caltech/IPAC.

We present 1.25–19 μm infrared spectra of pure solid CH4 and H2O/CH4=87, 20, and 3 solid mixtures at temperatures from 15 to 150 K. We compare and contrast the absorptions of CH4 in solid H2O with those of pure CH4. Changes in selected peak positions, profiles, and relative strength with temperature are presented, and absolute strengths for absorptions of CH4 in solid H2O are estimated. Using the two largest ( ν 3 + ν 4 ) and ( ν 1 + ν 4 ) near-IR absorptions of CH4 at 2.324 and 2.377 μm (4303 and 4207 cm−1), respectively, as examples, we show that peaks of CH4 in solid H2O are at slightly shorter wavelength (higher frequency) and broader than those of pure solid CH4. With increasing temperature, these peaks shift to higher frequency and become increasingly broad, but this trend is reversible on re-cooling, even though the phase transitions of H2O are irreversible. It is to be hoped that these observations of changes in the positions, profiles, and relative intensities of CH4 absorptions with concentration and temperature will be of use in understanding spectra of icy outer Solar System bodies.

We present spectra of Saturn's icy satellites Mimas, Enceladus, Tethys, Dione, Rhea, and Hyperion, 1.0–2.5 μm, with data extending to shorter (Mimas and Enceladus) and longer (Rhea and Dione) wavelengths for certain objects. The spectral resolution ( R = λ / Δ λ ) of the data shown here is in the range 800–1000, depending on the specific instrument and configuration used; this is higher than the resolution ( R = 225 at 3 μm) afforded by the Visual-Infrared Mapping Spectrometer on the Cassini spacecraft. All of the spectra are dominated by water ice absorption bands and no other features are clearly identified. Spectra of all of these satellites show the characteristic signature of hexagonal H2O ice at 1.65 μm. We model the leading hemisphere of Rhea in the wavelength range 0.3–3.6 μm with the Hapke and the Shkuratov radiative transfer codes and discuss the relative merits of the two approaches to fitting the spectrum. In calculations with both codes, the only components used are H2O ice, which is the dominant constituent, and a small amount of tholin (Ice Tholin II). Tholin in small quantities (few percent, depending on the mixing mechanism) appears to be an essential component to give the basic red color of the satellite in the region 0.3–1.0 μm. The quantity and mode of mixing of tholin that can produce the intense coloration of Rhea and other icy satellites has bearing on its likely presence in many other icy bodies of the outer Solar System, both of high and low geometric albedos. Using the modeling codes, we also establish detection limits for the ices of CO2 (a few weight percent, depending on particle size and mixing), CH4 (same), and NH4OH (0.5 weight percent) in our globally averaged spectra of Rhea's leading hemisphere. New laboratory spectral data for NH4OH are presented for the purpose of detection on icy bodies. These limits for CO2, CH4, and NH4OH on Rhea are also applicable to the other icy satellites for which spectra are presented here. The reflectance spectrum of Hyperion shows evidence for a broad, unidentified absorption band centered at 1.75 μm.

We present the mid-IR spectrum of 4-azachrysene (C17H11N) frozen in solid H2O at 14 K, data directly comparable to astronomical observations along dense cloud lines of sight. We tabulate the positions, profiles, and relative intensities of those 4-azachrysene peaks not obscured by strong H2O absorptions and note some significant changes in position and/or intensity relative to the previously published values for 4-azachrysene isolated in an argon matrix. In contrast to simple PAHs that do not interact strongly with solid H2O, PANHs, with their nitrogen atom(s), are potentially capable of hydrogen bonding with H2O, and this presumably gives rise to some of the spectral changes. This demonstrates that observers will not always be able to rely on peak positions of matrix isolated PANHs to correctly reflect the actual absorption band positions of PANHs along lines of sight where they will exist as pure solids or be frozen in H2O. In general these nitrogen heterocycles are of astrobiological interest since this class of molecules has been detected in meteorites, they could be pre-biotically important, and/or they could act as false biomarkers.

We present infrared (IR) spectral data from matrix isolation experiments and density functional theory calculations on the pre-biologically interesting molecule aminoacetonitrile, a precursor to glycine. We find that this nitrile has an unusually weak nitrile (C=N) stretch in the infrared, in contrast to expectations based on measurements and models of other nitriles under astrophysical conditions. The absence of an observable nitrile absorption feature in the infrared will make the IR search for this molecule considerably more difficult, and will raise estimates of upper limits on nitriles in interstellar and outer Solar System ices. This is also of relevance to assessing the formation routes of the amino acid glycine, since aminoacetonitrile is the putative precursor to glycine via the Strecker synthesis, the mechanism postulated to have produced the amino acids in meteorites.

We present mass spectra of the residual organic matter that results from the ultraviolet photolysis of realistic interstellar ice analogs in the laboratory. The mass spectra show that this residue is a complex mixture of high molecular weight organic molecules, reminiscent of those reported for interplanetary dust particles (IDPs) – asteroidal and cometary dust. This represents a further characterization of the material for which we have already reported amphiphilic properties (Dworkin et al., 2001). If we assume that the compounds observed are conjugated hydrocarbons, the mass spectra of the organics are consistent with organic compounds of up to 22 carbon atoms. Heating in air at low-pressure up to 1470 K as a simulation of atmospheric entry increases the molecular masses detected by lL 2 MS, resulting in a spectrum similar to those of the IDPs Florianus, and Aurelian. The results presented here are consistent with the notion that some of the large organic molecules delivered to the Earth on IDPs could have had their origin in low-temperature ice chemistry. Published by Elsevier Ltd on behalf of COSPAR.

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H,O ice under astrophysical conditions, and the products were analyzed using high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H,O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry reported here leads to specific predictions of the relative abundances of oxidized naphthalenes that should exist in meteorites. Since oxidized PAHs are present in meteorites and interplanetary dust particles, and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life. 0 2002 COSPAR. Published by Elsevier Science Ltd. All

We present the 2335-2325 cm-1 infrared spectra and band positions, profiles and strengths (A values) of solid nitrogen and binary mixtures of N2 with other molecules at 12 K. The data demonstrate that the strength of the infrared forbidden N2 fundamental near 2328 cm-1 is moderately enhanced in the presence of NH3, strongly enhanced in the presence of H2O and very strongly enhanced (by over a factor of 1000) in the presence of CO2, but is not significantly affected by CO, CH4, or O2. The mechanisms for the enhancements in N2-NH3 and N2-H2O mixtures are fundamentally different from those proposed for N2-CO2 mixtures. In the first case, interactions involving hydrogen-bonding are likely the cause. In the latter, a resonant exchange between the N2 stretching fundamental and the 18O = 12C asymmetric stretch of 18O12C16O is indicated. The implications of these results for several astrophysical issues are briefly discussed.

The infrared transmission spectra and photochemical behavior of various organic compounds isolated in solid N2 ices, appropriate for applications to Triton and Pluto, are presented. It is shown that excess absorption in the surface spectra of Triton and Pluto, i.e., absorption not explained by present models incorporating molecules already identified on these bodies (N2, CH4, CO, and CO2), that starts near 4450 cm-1 (2.25 micrometers) and extends to lower frequencies, may be due to alkanes (C(n)H2n+2) and related molecules frozen in the nitrogen. Branched and linear alkanes may be responsible. Experiments in which the photochemistry of N2:CH4 and N(2):CH4:CO ices was explored demonstrate that the surface ices of Triton and Pluto may contain a wide variety of additional species containing H, C, O, and N. Of these, the reactive molecule diazomethane, CH2N2, is particularly important since it may be largely responsible for the synthesis of larger alkanes from CH4 and other small alkanes. Diazomethane would also be expected to drive chemical reactions involving organics in the surface ices of Triton and Pluto toward saturation, i.e., to reduce multiple CC bonds. The positions and intrinsic strengths (A values) of many of the infrared absorption bands of N2 matrix-isolated molecules of relevance to Triton and Pluto have also been determined. These can be used to aid in their search and to place constraints on their abundances. For example, using these A values the abundance ratios CH4/N2 approximately 1.3 x 10(-3), C2H4/N2or = 9.5 x 10(-7) and H2CO/N2or = 7.8 x 10(-7) are deduced for Triton and CH4/N2 approximately 3.1 x 10(-3), C2H4/N2or = 4.1 x 10(-6), and H2CO/N2or = 5.2 x 10(-6) deduced for Pluto. The small amounts of C2H4 and H2CO in the surface ices of these bodies are in disagreement with the large abundances expected from many theoretical models.

We report the discovery of a series of infrared absorption bands between 3600 and 3100 cm -1 (2.8-3.2 μm) in the spectrum of Io. Individual narrow bands are detected at 3553, 3514.5, 3438, 3423, 3411.5, and 3401 cm -1 (2.815, 2.845, 2.909, 2.921, 2.931, and 2.940 μm, respectively). The positions and relative strengths of these bands, and the difference of their absolute strengths between the leading and trailing faces of Io, indicate that they are due to SO 2 . The band at 3438 cm -1 (2.909 μm) could potentially have a contribution from an additional molecular species. The existence of these bands in the spectrum of Io indicates that a substantial fraction of the SO 2 on Io must reside in transparent ices having relatively large crystal sizes. The decrease in the continuum observed at the high frequency ends of the spectra is probably due to the low frequency side of the recently detected, strong 3590 cm -1 (2.79 μm) feature. This band is likely due to the combination of a moderately strong SO 2 band and an additional absorption from another molecular species, perhaps H 2 O isolated in SO 2 at low concentrations. A broad (FWHM ≈ 40-60 cm -1 ), weak band is seen near 3160 cm -1 (3.16 μm) and is consistent with the presence of small quantities of H 2 O isolated in SO 2 -rich ices. There is no evidence in the spectra for the presence of H 2 O vapor on Io. Thus, the spectra presented here neither provide unequivocal evidence for the presence of H 2 O on Io nor preclude it at the low concentrations suggested by past studies.

A strong absorption band at 3590 +/- 20/cm (2.790 +/- 0.015 microns) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2 nu(sub 1) + nu(sub 3) comination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features at 3370 and 3170/cm (2.97 and 3.15 microns) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether there are two resolvable components.

Thermally promoted formaldehyde (H2CO) reactions in very low temperature ices have been studied to test their importance as a source of organic molecules in astrophysical environments such as comets and interstellar ices. The infrared absorption strengths of a number of the H2CO bands were measured in 10 K ices of pure H2CO and H20:H2CO = 100:3. Infrared spectroscopy was used to monitor the formaldehyde chemistry during warm-up of ices containing H2CO and one or more of the molecules H2O, CH3OH, CO, CO2, O2, and NH3. Formaldehyde reactions do not proceed at low temperatures in the absence of NH3. However, even small traces of NH3 (NH3/H2COor = 0.005) are sufficient to induce conversion of a considerable fraction (40%) of the H2CO into organic residues. Formaldehyde reactions were observed to start at temperatures as low as 40 K for NH3:H2CO binary ices and at approximately 80 K in astrophysically relevant (i.e., H2O-dominated) ices. A total of five different organic products of these reactions can be distinguished by infrared spectroscopy. One of them is polyoxymethylene (POM), a well-known H2CO polymerization product, whereas the others are reaction products of H2CO with H20, CH3OH and NH3. These all seem to be derivatives of polyoxymethylene. The nature of the components and their relative abundances depend strongly on the initial composition of the ice mixture as well as on the ice's irradiation history. We estimate that about 1% of the organics found in the coma of Comet Halley could have been produced by thermal formaldehyde reactions taking place in the nucleus.

The recent missions to Comet Halley detected large quantities of organic material on grains as well as organic molecules in the gas phase. A possible origin of these materials is the energetic processing of ice mantles on the grains prior to comet formation, either in the pre-solar nebula or the interstellar medium. This process was simulated in the laboratory by depositing interstellar ice analogs (H2O/CH3OH/CO/NH3) on a cold (10 K) substrate with simultaneous UV irradiation. The material evaporating during warm-up of the photolyzed ice as well as the residue remaining at room temperature was analyzed by a number of techniques. It was found that a large number of organic molecules of various complexity are synthesized during the simulation process, stressing the possible significance of UV photolysis for producing the organic Comet material.

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

Infrared spectra of Io in the region 2.5-5.0 micrometers, including new observational data, are analyzed using detailed laboratory studies of plausible surface ices. Besides the absorption bands attributable to sulfur dioxide frosts, four infrared spectral features of Io are shown to be unidentified. These unidentified features show spatial and temporal band strength variations. One pair is centered around 3.9 micrometers (3.85 and 3.91 micrometers) and the second pair is centered around 3.0 micrometers (2.97 and 3.15 micrometers). These absorptions fall close to the fundamental stretching modes in H2S and H2O, respectively. The infrared absorption spectra of an extensive set of laboratory ices ranging from pure materials, to binary mixtures of H2S and H2O (either mixed at different concentrations or layered), to H2O:H2S:SO2 mixtures are discussed. The effects of ultraviolet irradiation (120 and 160 nm) and temperature variation (from 9 to 130 K) on the infrared spectra of the ices are examined. This comparative study of Io reflectance spectra with the laboratory mixed ice transmission data shows the following: (1) Io's surface most likely contains H2S and H2O mixed with SO2. The 3.85- and 3.91-micrometers bands in the Io spectra can be accounted for by the absorption of the S-H stretching vibration (nu 1) in H2S clusters and isolated molecules in an SO2-dominated ice. The weak 2.97- and 3.15-micrometers bands which vary spatially and temporally in the Io spectra coincide with the nu 3 and nu 1 O-H stretching vibrations of clusters of H2O molecules complexed, through hydrogen bonding and charge transfer interactions, with SO2. (2) The observations are well matched qualitatively by the transmission spectra of SO2 ices containing about 3% H2S and 0.1% H2O which have been formed by the condensation of a mixture of the gases onto a 100 K surface. (3) No new features are produced in the region 2.5 to 5.0 micrometers in the spectrum of these ices under prolonged ultraviolet irradiation or temperature variation up to 120 K. (4) Comparison of the Io spectra to transmission spectra of both mixed molecular ices and layered ices indicates that only the former can explain the shifts and splitting of the absorption bands seen in the Io spectrum and additionally can account for the fact that solid H2S is observed in the surface material of Io at temperature and pressure conditions above the sublimation point of pure H2S.

Infrared transmission spectra from 53 meteorites in the spectral range from 2.5 to 25 μm were measured to permit comparisons with data of astronomical objects that are potential meteorite sources. Data were taken for 14 carbonaceous chondrites, 5 LL ordinary chondrites, 6 L ordinary chondrites, 10 H ordinary chondrites, 1 enstatite chondrite, 4 aubrites, 3 eucrites, 4 howardites, 1 diogenite, 1 mesosiderite, 2 nakhlites, 1 shergottite, and the anomalous achondrite Angra dos Reis. The CO and CV carbonaceous chondrites have spectra similar to each other, with 10-μm features characteristic of olivine. The CM carbonaceous chondrites have distinctive 10-μm features that are attributed to layer lattice silicates. Members of both the CI and CR classes have spectra distinct from those of other carbonaceous chondrites. The LL, L, and H ordinary chondrites have spectra that match those of olivine and pyroxene mixtures. The enstatite chondrites and enstatite achondrites (aubrites) all exhibit spectra diagnostic of the pyroxene enstatite. The angrite, howardites, aucrites, nakhlites, shergottite, and diogenite all have similar spectra also dominated by pyroxene. The single mesosiderite examined had a spectrum distinct from all the other meteorites.

IR spectroscopy has been used to ascertain several parameters associated with CO, H2O, and H2O:CO ices' physical behavior. Since CO is noted to be capable of condensing into H2O-rich ices at temperatures that are twice as high as those required for condensation in pure CO, CO is able to condense onto H2O-rich ice grains at temperatures of up to 50 K. CO's presence in H2O ice modestly enhances the effective volatility of the H2O. Attention is given to the implications of these results for cometary models generally and the question of cometary formation specifically.

The possibility is explored whether an IDP (interplanetary dust particle) is cometary or asteroidal from measurements of the solar flare track density within its constituent mineral grains. Dust particles that are larger than 1 micron, when injected into the Solar System from comets and asteroids, will spiral into the sun due to the Poynting-Robertson effect. During the process of spiraling in, such dust particles accumulate solar flare tracks. The accumulated track density for a given dust grain is a function of the duration of its space exposure and its distance from the sun. Using a computer model, it was determined that the expected track density distributions from grains produced by comets are very different from those produced by asteroids. Individual asteroids produce populations of particles that arrive at 1 AU with scaled track density distributions containing 'spikes,' while comets supply particles with a flatter and wider distribution of track densities.

We have attempted to incorporate the compositional information available from interplanetary dust particles (IDPs) and the recent Halley flybys into a coherent model to account for cometary infrared emission. We show that the entire infrared emission spectrum of Comet Halley is consistent with the presence of three general dust particle types. These dust types are (i) amorphous carbon grains, (ii) crystalline silicate grains, and (iii) crystalline silicate grains with thin carbonaceous coatings. In analogy with IDPs, the thin carbonaceous coatings on the silicate minerals may be responsible for the dark appearance of most comets. Good fits to the observational data are found for particle populations having particle size distributions similar to those inferred for Comet Halley, and silicate to amorphous carbon mass ratios of 8 to 40, values consistent with IDP and flyby data. Composite particles in which all the carbon resides in thick mantles on silicate cores fail to simultaneously match both the spectral and compositional constraints. Finally, the apparent strength of the 10-μm silicate feature is found to be particle size dependent. Consequently, as has been noted before, the absence of an obvious 10-μm feature in other comets does not imply the absence of silicates, but may instead imply the dominance of large silicate grains.

The photochemical and thermal evolution of H2O-, CH3OH-, NH3-, and CO-containing ices whose relative proportions in mixture are consistent with those of interstellar ice are presently studied experimentally. The UV photolysis of these ice analogs invariably generates H2CO, CO2, CO, CH4, and HCO, largely through the photofragmentation of CH3OH. CO and CH4 leave the samples as warmup proceeds to 100 K; most of the parent ice molecules are found to have sublimed upon the reaching of 200 K, with only a mixture of more refractory substances remaining. A residue of CH2 groups remains even after warmup to 300 K.

The majority of the interplanetary dust particles (IDPs) collected in the stratosphere belong to one of three major classes, the first two dominated by the anhydrous minerals olivine and pyroxene, and the third by hydrous layer-lattice silicates. Infrared spectroscopy and transmission electron microscopy studies show that the different IDP classes represent different types of dust that exist as individual particles in interplanetary space. The majority of the collected IDPs smaller than 30 micrometers in diameter in the layer-lattice silicate and pyroxene classes appear not to have been heated to temperatures above 600 degrees C during atmospheric entry. The relatively low maximum temperatures experienced by these IDPs during atmospheric entry imply that they arrive at the top of the atmosphere with low geocentric encounter velocities. This limits the possible encounter trajectories for these particles to relatively circular, prograde orbits. As a result, it is unlikely that these IDPs are from Earth-crossing comets or asteroids. Asteroids, and comets having low inclinations and perihelia outside 1.2 AU, appear to be the best candidates for the parent bodies of the pyroxene and layer-lattice silicate particles. Chemical and mineralogical information suggests that the pyroxene-rich IDPs are from comets and the layer-lattice silicate-rich IDPs are from asteroids. The collected IDPs dominated by olivine appear to include a larger fraction of particles heating above 600 degrees C, suggesting that these particles were captured from more eccentric orbits. This, and the observation of the infrared spectral features of olivine in several comets suggest these particles have a cometary origin. Since much of the collected dust has apparently been captured from nearly circular, prograde orbits and since there are no appropriate parent bodies presently in such orbits, these results provide an experimental confirmation that the Poynting-Robertson effect exists as a nongravitational force important in the orbital evolution of dust in the Solar System.