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Ices at ∼15 K consisting of the polycyclic aromatic hydrocarbon coronene (C24H12) condensed either with H2O, CO2, or CO in the ratio of 1 : 100 or greater have been subjected to MeV proton bombardment from a Van de Graaff generator. The resulting reaction products have been examined by infrared transmissionreflection-transmission spectroscopy and by microprobe laser-desorption laser-ionization mass spectrometry. Just as in the case of UV photolysis, oxygen atoms are added to coronene, yielding, in the case of H2O ices, the addition of one or more alcohol ( i OH) and ketone (1CuO) side chains to the coronene scaffolding. There are, however, significant differences between the products formed by proton irradiation and the products formed by UV photolysis of coronene containing CO and CO2 ices. The formation of a coronene carboxylic acid ( i COOH) by proton irradiation is facile in solid CO but not in CO2, the reverse of what was previously observed for UV photolysis under otherwise identical conditions. This work presents evidence that cosmicray irradiation of interstellar or cometary ices should have contributed to the formation of aromatics bearing ketone and carboxylic acid functional groups in primitive meteorites and interplanetary dust particles. Subject headings: astrobiology — astrochemistry — comets: general — cosmic rays — ISM: molecules — molecular processes

Ultraviolet photolysis of various coronene-ice mixtures at low temperature and pressure caused the addition of amino (”NH2), methyl (”CH3), methoxy (”OCH3), cyano/isocyano (”CN, ”NC), and acid (”COOH) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C24H12), in addition to previously reported alcohol (”OH) and ketone (>C»O) formation. This work represents the first experimental evidence that ice photochemistry may have contributed to the aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest that a wide range of modified PAHs should be expected in interstellar ices and materials that predated solar system formation. The implications of these results for interstellar and meteoritic chemistry are discussed. Subject headings: astrobiology — astrochemistry — ISM: molecules — meteors, meteoroids — molecular processes — ultraviolet: ISM

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

Seven particles captured by the Stardust Interstellar Dust Collector and returned to Earth for laboratory analysis have features consistent with an origin in the contemporary interstellar dust stream. More than 50 spacecraft debris particles were also identified. The interstellar dust candidates are readily distinguished from debris impacts on the basis of elemental composition and/or impact trajectory. The seven candidate interstellar particles are diverse in elemental composition, crystal structure, and size. The presence of crystalline grains and multiple iron-bearing phases, including sulfide, in some particles indicates that individual interstellar particles diverge from any one representative model of interstellar dust inferred from astronomical observations and theory.

Hard X-ray, quantitative, fluorescence elemental imaging was performed on the ID22NI nanoprobe and ID22 microprobe beam lines of the European Synchrotron Research facility (ESRF) in Grenoble, France, on eight interstellar candidate impact features in the framework of the NASA Stardust Interstellar Preliminary Examination (ISPE). Three features were unambiguous tracks, and the other five were identified as possible, but not definite, impact features. Overall, we produced an absolute quantification of elemental abundances in the 15 ? Z ? 30 range by means of corrections of the beam parameters, reference materials, and fundamental atomic parameters. Seven features were ruled out as interstellar dust candidates (ISDC) based on compositional arguments. One of the three tracks, I1043,1,30,0,0, contained, at the time of our analysis, two physically separated, micrometer-sized terminal particles, the most promising ISDCs, Orion and Sirius. We found that the Sirius particle was a fairly homogenous Ni-bearing particle and contained about 33 fg of distributed high-Z elements (Z > 12). Orion was a highly heterogeneous Fe-bearing particle and contained about 59 fg of heavy elements located in hundred nanometer phases, forming an irregular mantle that surrounded a low-Z core. X-ray diffraction (XRD) measurements revealed Sirius to be amorphous, whereas Orion contained partially crystalline material (Gainsforth et al. 2014). Within the mantle, one grain was relatively Fe-Ni-Mn-rich; other zones were relatively Mn-Cr-Ti-rich and may correspond to different spinel populations. For absolute quantification purposes, Orion was assigned to a mineralogical assemblage of forsterite, spinel, and an unknown Fe-bearing phase, while Sirius was most likely composed of an amorphous Mg-bearing material with minor Ni and Fe. Owing to its nearly chondritic abundances of the nonvolatile elements Ca, Ti, Co, and Ni with respect to Fe, in combination with the presence of olivine and spinel as inferred from XRD measurements, Orion had a high probability of being extraterrestrial in origin.

We discuss the inherent difficulties that arise during "ground truth" characterization of the Stardust interstellar dust collector. The challenge of identifying contemporary interstellar dust impact tracks in aerogel is described within the context of background spacecraft secondaries and possible interplanetary dust particles and beta-meteoroids. In addition, the extraction of microscopic dust embedded in aerogel is technically challenging. Specifically, we provide a detailed description of the sample preparation techniques developed to address the unique goals and restrictions of the Interstellar Preliminary Exam. These sample preparation requirements and the scarcity of candidate interstellar impact tracks exacerbate the difficulties. We also illustrate the role of initial optical imaging with critically important examples, and summarize the overall processing of the collection to date.

–Here, we report the identification of 69 tracks in approximately 250 cm 2 of aerogelcollectors of the Stardust Interstellar Dust Collector. We identified these tracks throughStardust@home, a distributed internet-based virtual microscope and search engine, in which> 30,000 amateur scientists collectively performed >9 9 10 7 searches on approximately 10 6 fields of view. Using calibration images, we measured individual detection efficiency, andfound that the individual detection efficiency for tracks > 2.5 lm in diameter was >0.6, andwas >0.75 for tracks >3 lm in diameter. Because most fields of view were searched >30times, these results could be combined to yield a theoretical detection efficiency near unity.The initial expectation was that interstellar dust would be captured at very high speed. Theactual tracks discovered in the Stardust collector, however, were due to low-speed impacts,and were morphologically strongly distinct from the calibration images. As a result, thedetection efficiency of these tracks was lower than detection efficiency of calibrationspresented in training, testing, and ongoing calibration. Nevertheless, as calibration imagesbased on low-speed impacts were added later in the project, detection efficiencies for low-speed tracks rose dramatically. We conclude that a massively distributed, calibrated search,with amateur collaborators, is an effective approach to the challenging problem ofidentification of tracks of hypervelocity projectiles captured in aerogel.1510 A. J. Westphal et al.

Under the auspices of the Stardust Interstellar Preliminary Examination, picokeystones extracted from the Stardust Interstellar Dust Collector were examined with synchrotron Fourier transform infrared (FTIR) microscopy to establish whether they contained extraterrestrial organic material. The picokeystones were found to be contaminated with varying concentrations and speciation of organics in the native aerogel, which hindered the search for organics in the interstellar dust candidates. Furthermore, examination of the picokeystones prior to and post X-ray microprobe analyses yielded evidence of beam damage in the form of organic deposition or modification, particularly with hard X-ray synchrotron X-ray fluorescence. From these results, it is clear that considerable care must be taken to interpret any organics that might be in interstellar dust particles. For the interstellar candidates examined thus far, however, there is no clear evidence of extraterrestrial organics associated with the track and/or terminal particles. However, we detected organic matter associated with the terminal particle in Track 37, likely a secondary impact from the Al-deck of the sample return capsule, demonstrating the ability of synchrotron FTIR to detect organic matter in small particles within picokeystones from the Stardust interstellar dust collector.

On the basis of an interstellar dust model compatible with Ulysses and Galileo observations, we calculate and predict the trajectories of interstellar dust (ISD) in the solar system and the distribution of the impact speeds, directions, and flux of ISD particles on the Stardust Interstellar Dust Collector during the two collection periods of the mission. We find that the expected impact velocities are generally low (less than 10 km per second) for particles with the ratio of the solar radiation pressure force to the solar gravitational force beta greater than 1, and that some of the particles will impact on the cometary side of the collector. If we assume astronomical silicates for particle material and a density of 2 grams per cubic centimeter, and use the Ulysses measurements and the ISD trajectory simulations, we conclude that the total number of (detectable) captured ISD particles may be on the order of 50. In companion papers in this volume, we report the discovery of three interstellar dust candidates in the Stardust aerogel tiles. The impact directions and speeds of these candidates are consistent with those calculated from our ISD propagation model, within the uncertainties of the model and of the observations.

Using synchrotron-based X-ray diffraction measurements, we identified crystalline material in two particles of extraterrestrial origin extracted from the Stardust Interstellar Dust Collector. The first particle, I1047,1,34 (Hylabrook), consisted of a mosaiced olivine grain approximately 1 mu m in size with internal strain fields up to 0.3%. The unit cell dimensions were a - 4.85 +/- 0.08 angstrom, b - 10.34 +/- 0.16 angstrom, c - 6.08 +/- 0.13 angstrom (2 sigma). The second particle, I1043,1,30 (Orion), contained an olivine grain approximate to 2 mu m in length and > 500 nm in width. It was polycrystalline with both mosaiced domains varying over approximate to 20 degrees and additional unoriented domains, and contained internal strain fields < 1%. The unit cell dimensions of the olivine were a = 4.76 +/- 0.05 angstrom, b = 10.23 +/- 0.10 angstrom, c = 5.99 +/- 0.06 angstrom (2 sigma), which limited the olivine to a forsteritic composition [Fo(65) (2 sigma). Orion also contained abundant spinel nanocrystals of unknown composition, but unit cell dimension a = 8.06 +/- 0.08 angstrom (2 sigma). Two additional crystalline phases were present and remained unidentified. An amorphous component appeared to be present in both these particles based on STXM and XRF results reported elsewhere.

We report the quantitative characterization by synchrotron soft X-ray spectroscopy of 31 potential impact features in the aerogel capture medium of the Stardust Interstellar Dust Collector. Samples were analyzed in aerogel by acquiring high spatial resolution maps and high energy-resolution spectra of major rock-forming elements Mg, Al, Si, Fe, and others. We developed diagnostic screening tests to reject spacecraft secondary ejecta and terrestrial contaminants from further consideration as interstellar dust candidates. The results support an extraterrestrial origin for three interstellar candidates: I1043,1,30 (Orion) is a 3 pg particle with Mg-spinel, forsterite, and an iron-bearing phase. I1047,1,34 (Hylabrook) is a 4 pg particle comprising an olivine core surrounded by low-density, amorphous Mg-silicate and amorphous Fe, Cr, and Mn phases. I1003,1,40 (Sorok) has the track morphology of a high-speed impact, but contains no detectable residue that is convincingly distinguishable from the background aerogel. Twenty-two samples with an anthropogenic origin were rejected, including four secondary ejecta from impacts on the Stardust spacecraft aft solar panels, nine ejecta from secondary impacts on the Stardust Sample Return Capsule, and nine contaminants lacking evidence of an impact. Other samples in the collection included I1029,1,6, which contained surviving solar system impactor material. Four samples remained ambiguous: I1006,2,18, I1044,2,32, and I1092,2,38 were too dense for analysis, and we did not detect an intact projectile in I1044,3,33. We detected no radiation effects from the synchrotron soft X-ray analyses; however, we recorded the effects of synchrotron hard X-ray radiation on I1043,1,30 and I1047,1,34.

Laboratory experiments have shown that the UV photo-irradiation of low-temperature ices of astrophysical interest leads to the formation of organic molecules, including molecules important for biology such as amino acids, quinones, and amphiphiles. When pyrimidine is introduced into these ices, the products of irradiation include the nucleobases uracil, cytosine, and thymine, the informational sub-units of DNA and RNA, as well as some of their isomers. The formation of these compounds, which has been studied both experimentally and theoretically, requires a succession of additions of OH, NH2, and CH3 groups to pyrimidine. Results show that H2O ice plays key roles in the formation of the nucleobases, as an oxidant, as a matrix in which reactions can take place, and as a catalyst that assists proton abstraction from intermediate compounds. As H2O is also the most abundant icy component in most cold astrophysical environments, it probably plays the same roles in space in the formation of biologically relevant compounds. Results also show that although the formation of uracil and cytosine from pyrimidine in ices is fairly straightforward, the formation of thymine is not. This is mostly due to the fact that methylation is a limiting step for its formation, particularly in H2O-rich ices, where methylation must compete with oxidation. The relative inefficiency of the abiotic formation of thymine to that of uracil and cytosine, together with the fact that thymine has not been detected in meteorites, are not inconsistent with the RNA world hypothesis. Indeed, a lack of abiotically produced thymine delivered to the early Earth may have forced the choice for an RNA world, in which only uracil and cytosine are needed, but not thymine.

Organic compounds observed in the interstellar medium and in solar system bodies are of particular importance for revealing the chemistry that may have led to life’s origin. Among these compounds, amino acids may have played a crucial role since they are basic components of proteins, which are the essential constituents of all organisms. We present laboratory studies testing the stability of amino acids against ultraviolet (UV) photolysis. Two biological and two nonbiological amino acids have been irradiated in frozen Ar, N2, and H2O to simulate conditions in the interstellar gas and on interstellar grains. The experimental results can be interpreted to indicate that amino acids in the gas phase will likely be destroyed during the lifetime of a typical interstellar cloud. In regions with relatively low UV radiation, amino acids might be present as transient gas-phase species. Their survival in interstellar icy grain mantles and the surface layers of comets and planets is strongly limited in the presence of UV irradiation. The rate of destruction is rather insensitive to the amino acid structure and to the ice matrix. We consider the implications of these results for the survival and transfer of amino acids in space environments, and thus their possible availability for prebiotic chemistry. Subject headings: infrared: ISM: lines and bands — ISM: abundances — ISM: molecules — methods: laboratory — molecular processes

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), 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.

We present 2338-2322 per centimeter (4.277-4.307 micrometer) infrared spectra of a number of N2-containing mixed molecular ices and demonstrate that the strength of the infrared "forbidden" band due to the N=N stretch near 2328 per centimeter (4.295 micrometer) is extremely sensitive to the composition of the ice. The strength of the 2328 per centimeter N2 fundamental is significantly enhanced relative to that of pure N2 ice when NH3, H2O, or CO2 are present, but is largely unaffected by the presence of CO, CH4 or O2. We use the laboratory data in coil junction with ISO data that probes several lines-of-sight through dense molecular clouds to place limits on the abundance of interstellar solid phase N2 and the composition of the ices. Deriving upper limits is complicated by the presence of overlapping absorptions due to CO2 gas in the clouds and, in some cases, to photospheric CO in the background star. These upper limits are just beginning to be low enough to constrain interstellar grain models and the composition of possible N2-bearing interstellar ices. We outline the search criteria that will need to be met if solid interstellar N2 is to be detected in the future. We also discuss some of the implications of the presence of warm CO2 gas along the lines-of-sight to embedded protostars and demonstrate that its presence may help resolve certain puzzles associated with the previously derived gas/solid CO2 ratios and the relative abundances of polar and nonpolar ices towards these objects. Finally, we briefly comment on the possible implications of these results for the interpretation of N2 detections on outer solar system bodies.

Interstellar gas and dust constitute the primary material from which the solar system formed. Near the end of the hot early phase of star and planet formation, volatile, less refractory materials were transported into the inner solar system as comets and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall seeded them with complex organic compounds [Oró, J. (1961) Nature (London) 190, 389–390; Delsemme, A. H. (1984) Origins Life 14, 51–60; Anders, E. (1989) Nature (London) 342, 255–257; Chyba, C. F. & Sagan, C. (1992) Nature (London) 355, 125–131]. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by UV photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

To better understand the chemical species that gives rise to the 2165 cm-1 (4.62 μm) "XCN" absorption feature seen toward embedded protostars such as W33A, we have performed laboratory studies using deuterium (2H) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of 13C, 15N, and 18O labeling experiments that are consistent with previously reported values.

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.

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of a methyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H and C triple bond N stretches near 2900 and 2200 cm-1, respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron-withdrawing group induces sufficient partial charge on the ring to give the neutral molecule spectra characteristics of the anthracene cation. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than those for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.

Matrix isolation techniques have been used to measure the mid-infrared spectra of the polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, phenanthrene, 1,2-benzanthracene, chrysene, pyrene, tetracene, and triphenylene. The band positions and relative strengths are compared to previous laboratory studies, where available, and with available theoretical calculations.1 Comparisons with theory indicate that density functional theory (DFT) does an excellent job of describing the majority of the infrared active fundamentals of the PAHs considered here. Band positions typically match to within 5 cm-1, with the worst mismatches usually no more than 15 cm-1. Matches in band strengths are not as precise but, with the exception of the CH stretching bands, are generally good to better than 35% for most strong and moderate bands and to factors of 2 to 3 for weaker bands. Theory predicts CH stretching band strengths that are about a factor of 2 times too strong. The laboratory spectra contain large numbers...

Matrix isolation techniques have been used to measure the 4000−500 cm-1 infrared spectra of the polycyclic aromatic hydrocarbons (PAHs) fluoranthene, benzo[a]fluoranthene, benzo[b]fluoranthene, benzo[j]fluoranthene, benzo[k]fluoranthene, and benzo[ghi]fluoranthene. For the PAHs where previous matrix isolation and gas-phase laboratory studies are available, agreements between the data sets are generally very good. While the fluoranthenes as a class produce infrared spectra that share many of the same characteristics of the spectra of PAHs containing only benzenoid moieties, for comparably sized molecules, the fluoranthenes tend to produce more absorption bands overall and considerably more and stronger bands in the 1550−1350 cm-1 range. These differences are largely due to the presence of the five-membered cyclopentadienyl ring characteristic of the family.

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of perdeuterated naphthalene, phenanthrene, pyrene, and chrysene. We also report matrix-isolation spectra for these four species. The theoretical and experimental frequencies and relative intensities for the perdeuterated species are in generally good agreement. The effect of perdeuteration is to reduce the sum of the integrated intensities by a factor of about 1.75. This reduction occurs for all vibrational motions, except for the weak low-frequency ring deformation modes. There is also a significant redistribution of the relative intensities between the out-of-plane C−D bands relative to those found for the out-of-plane C−H bands. The theoretical isotopic ratios provide an excellent diagnostic of the degree of C−H(C−D) involvement in the vibrational bands, allowing in most cases a clear distinction of the type of motion.

We present the 2320-2050 cm-1 (4.31-4.88 micrometers) infrared spectra of 16 solid-state nitriles, isonitriles, and related compounds in order to facilitate the assignment of absorption features in a spectral region now becoming accessible to astronomers for the first time through the Infrared Space Observatory (ISO). This frequency range spans the positions of the strong C triple bond N stretching vibration of these compounds and is inaccessible from the ground due to absorption by CO2 in the terrestrial atmosphere. Band positions, profiles, and intrinsic strengths (A values) were measured for compounds frozen in Ar and H2O matrices at 12 K. The molecular species examined included acetonitrile, benzonitrile (phenylcyanide), 9-anthracenecarbonitrile, dimethylcyanamide, isopropylnitrile (isobutyronitrile), methylacrylonitrile, crotononitrile, acrylonitrile (vinyl cyanide), 3-aminocrotononitrile, pyruvonitrile, dicyandiamide, cyanamide, n-butylisocyanide, methylisocyanoacetate, diisopropylcarbodiimide, and hydrogen cyanide. The C triple bond N stretching bands of the majority of nitriles fall in the 2300-2200 cm-1 (4.35-4.55 micrometers) range and have similar positions in both Ar and H2O matrices, although the bands are generally considerably broader in the H2O matrices. In contrast, the isonitriles and a few exceptional nitriles and related species produce bands at lower frequencies spanning the 2200-2080 cm-1 (4.55-4.81 micrometers) range. These features also have similar positions in both Ar and H2O matrices, and the bands are broader in the H2O matrices. Three of the compounds (pyruvonitrile, dicyandiamide, and cyanamide) show unusually large shifts of their C triple bond N stretching frequencies when changing from Ar to H2O matrices. We attribute these shifts to the formation of H2O:nitrile complexes with these compounds. The implications of these results for the identification of the 2165 cm-1 (4.62 micrometers) "XCN" interstellar feature and the 4550 cm-1 (2.2 micrometers) feature of various objects in the solar system are discussed.

Infrared observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the building blocks of comets. Since comets are thought to be a major source of the volatiles on the primative earth, their organic inventory is of central importance to questions concerning the origin of life. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, CH4, H2, and probably some NH3and H2CO, as well as more complex species including nitriles, ketones, and esters. The evidence for these, as well as carbonrich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon is briefly reviewed. This is followed by a detailed summary of interstellar/precometary ice photochemical evolution based on laboratory studies of realistic polar ice analogs. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and the moderately complex organic molecules: CH3CH2OH (ethanol), HC(= O)NH2(formamide), CH3C(= O)NH2(acetamide), R-CN (nitriles), and hexamethylenetetramine (HMT, C6H12N4), as well as more complex species including polyoxymethylene and related species (POMs), amides, and ketones. The ready formation of these organic species from simple starting mixtures, the ice chemistry that ensues when these ices are mildly warmed, plus the observation that the more complex refractory photoproducts show lipid-like behavior and readily self organize into droplets upon exposure to liquid water suggest that comets may have played an important role in the origin of life.

Dr. Derek Sears, the editor of the journal Meteoritics and Planetary Science, has established a policy of having each issue of the journal contain an invited review of an area that he deems to be of special cur-rent importance. Typically 20 to 25 pages of the beginning of the journal are devoted to each review. He has asked me to prepare such a review summarizing what we know about the composition and structure of interstellar materials. The attached paper is the result. This is a good time for such a review since tremendous progress has been made in the field of interstellar dust in recent years through the use of telescopic observations, theoretical studies, laboratory studies of analogs, and the study of actual interstellar samples found in meteorites. It is increasing clear that the interstellar medium (ISM) contains an enormous diversity of materials created by a wide range of chemical and physical processes. This understanding is a far cry from the picture of interstellar materials held as recently as two decades ago, a picture which incorporated only a few generic types of grains and few molecules. In the paper I review our current knowledge of the more abundant materials thought to exist in the ISM. The review concentrates on matter in interstellar dense molecular clouds since it is the materials in these environments from which new stars and planetary systems are formed, although materials in circumstellar environments and in the diffuse ISM are also discussed. The paper focuses largely on solid materials since they contain a major fraction of the heavier elements in clouds and because solids are most likely to survive incorporation into new planetary systems in identifiable form. The paper concludes with discussion of some of the implications resulting from the identification of these interstellar materials. I also present some new thoughts, the most intriguing being that meteoritic 'microdiamonds' may be the same material that modelers of the interstellar extinction call graphite! If my suggestion is correct it will help resolve the dilemma associated with the current over-subscription of cosmic C and should lead to some new approaches to both extinction models and the study of meteoritic interstellar microdiamonds.

Virtually everyone who works in a scientific field will ultimately have to deal, in one way or another, with the production of a Press Release. The importance of Press Releases cannot be over-estimated since it is by their distribution (and the distribution of the short science news articles that are generated from them by randomly scrambling their words) that the majority of the public learn of current scientific progress. Not surprisingly, a great deal of energy, time, and resources are spent each year in the production of these releases. Shortly after the start of a new year1 it occurred to us that this important task could be greatly simplified. We noted in a comprehensive survey of articles from 1983-2001 that 87.3% of the Press Releases and science news articles could be faithfully reproduced through the straightforward application of a set of simple standardized rules.2 These rules can be easily applied to generate a form containing a pre-written Press Release in which one need only fill in various blanks with items specific to the matter at hand in order to generate a full-blown Press Release.

The Meteor That Fell to Earth In April 2012, a meteor was witnessed over the Sierra Nevada Mountains in California. Jenniskens et al. (p. 1583 ) used a combination of photographic and video images of the fireball coupled with Doppler weather radar images to facilitate the rapid recovery of meteorite fragments. A comprehensive analysis of some of these fragments shows that the Sutter's Mill meteorite represents a new type of carbonaceous chondrite, a rare and primitive class of meteorites that contain clues to the origin and evolution of primitive materials in the solar system. The unexpected and complex nature of the fragments suggests that the surfaces of C-class asteroids, the presumed parent bodies of carbonaceous chondrites, are more complex than previously assumed.

Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases-the information subunits of DNA and RNA-are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab initio calculations have already shown that the irradiation of pyrimidine in pure H(2)O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH(3):pyrimidine and H(2)O:NH(3):pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

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.

Ionized polycyclic aromatic hydrocarbons (PAHs) are thought to constitute an important component of the interstellar medium. Despite this fact, the infrared spectroscopic properties of ionized PAHs are almost unknown. The results we present here derive from our ongoing spectroscopic study of matrix isolated PAH ions and include the spectra of the naphthalene cation, C10H8(+), and its fully deuterated analog, C10D8(+), between 4000 and 200/cm. Ions are generated by in situ Lyman-alpha photoionization of the neutral precursor. Bands of the C10H8(+) ion are observed at 1525.7, 1518.8, 1400.9, 1218.0, 1216.9, 1214.9, 1023.2, and 758.7/cm. Positions and relative intensities of these bands agree well with those in the available literature. The 758.7/cm band has not previously been reported. C10D8(+) ion bands appear at 1466.2, 1463.8, 1379.4, 1373.8, 1077.3, 1075.4, and 1063.1/cm. Compared to the analogous modes in the neutral molecule, the intensities of the cation's CC modes are enhanced by an order of magnitude, while CH modes are depressed by this same factor. Integrated absorption intensities are calculated for the strongest bands of C10H8 and for the observed bands of C10H8(+). Absolute intensities derived for the naphthalene cation differ from earlier experimental results by a factor of approximately 50, and from theoretical predictions by a factor of approximately 300. Reasons for these discrepancies and from the astronomical implications of PAH cation spectra are discussed.

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.

Multidimensional solid-state NMR spectroscopy is used to refine the identification and abundance determination of functional groups in insoluble organic matter (IOM) isolated from a carbonaceous chondrite (Murchison, CM2). It is shown that IOM is composed primarily of highly substituted single ring aromatics, substituted furan/pyran moieties, highly branched oxygenated aliphatics, and carbonyl groups. A pathway for producing an IOM-like molecular structure through formaldehyde polymerization is proposed and tested experimentally. Solid-state 13 C NMR analysis of aqueously altered formaldehyde polymer reveals considerable similarity with chondritic IOM. Carbon X-ray absorption near edge structure spectroscopy of formaldehyde polymer reveals the presence of similar functional groups across certain Comet 81P/Wild 2 organic solids, interplanetary dust particles, and primitive IOM. Variation in functional group concentration amongst these extraterrestrial materials is understood to be a result of various degrees of processing in the parent bodies, in space, during atmospheric entry, etc. These results support the hypothesis that chondritic IOM and cometary refractory organic solids are related chemically and likely were derived from formaldehyde polymer. The fine-scale morphology of formaldehyde polymer produced in the experiment reveals abundant nanospherules that are similar in size and shape to organic nanoglobules that are ubiquitous in primitive chondrites.

This paper presents spectra in the 2 to 20 micron range of quiescent cloud material located in the IC 5146 cloud complex. The spectra were obtained with NASA's Infrared Telescope Facility (IRTF) SpeX instrument and the Spitzer Space Telescope's Infrared Spectrometer. We use these spectra to investigate dust and ice absorption features in pristine regions of the cloud that are unaltered by embedded stars. We find that the H2O-ice threshold extinction is 4.03+/-0.05 mag. Once foreground extinction is taken into account, however, the threshold drops to 3.2 mag, equivalent to that found for the Taurus dark cloud, generally assumed to be the touchstone quiescent cloud against which all other dense cloud and embedded young stellar object observations are compared. Substructure in the trough of the silicate band for two sources is attributed to CH3OH and NH3 in the ices, present at the ~2% and ~5% levels, respectively, relative to H2O-ice. The correlation of the silicate feature with the E(J-K) color excess is found to follow a much shallower slope relative to lines of sight that probe diffuse clouds, supporting the previous results by Chiar et al. (2007)., 13 pages, 13 figures with multiple parts, accepted for publication in Astrophysical Journal, Feb. 2011

The mid-infrared (4000-450 cm-1; 2.5-22.2 micrometers) transmission spectra of seven Antarctic ureilites and 10 Antarctic H-5 ordinary chondrites are presented. The ureilite spectra show a number of absorption bands, the strongest of which is a wide, complex feature centered near 1000 cm-1 (10 micrometers) due to Si-O stretching vibrations in silicates. The profiles and positions of the substructure in this feature indicate that Mg-rich olivines and pyroxenes are the main silicates responsible. The relative abundances of these two minerals, as inferred from the spectra, show substantial variation from meteorite to meteorite, but generally indicate olivine is the most abundant (olivine:pyroxene = 60:40 to 95:5). Both the predominance of olivine and the variable olivine-to-pyroxene ratio are consistent with the known composition and heterogeneity of ureilites. The H-5 ordinary chondrites spanned a range of weathering classes and were used to provide a means of addressing the extent to which the ureilite spectra may have been altered by weathering processes. It was found that, while weathering of these meteorites produces some weak bands due to the formation of small amounts of carbonates and hydrates, the profile of the main silicate feature has been little affected by Antarctic exposure in the meteorites studied here. The mid-infrared ureilite spectra provide an additional means of testing potential asteroidal parent bodies for the ureilites. At present, the best candidates include the subset of S-type asteroids having low albedos and weak absorption features in the near infrared.

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.

Stardust, a NASA Discovery-class mission, was the first sample-return mission to return solid samples from beyond the Moon. Stardust was effectively two missions in one spacecraft: it returned the first materials from a known primitive solar system body, the Jupiter-family comet Wild 2; Stardust also returned a collector that was exposed to the contemporary interstellar dust stream for 200 days during the interplanetary cruise. Both collections present severe technical challenges in sample preparation and in analysis. By far the largest collection is the cometary one: approximately 300 micro g of material was returned from Wild 2, mostly consisting of approx. 1 ng particles embedded in aerogel or captured as residues in craters on aluminum foils. Because of their relatively large size, identification of the impacts of cometary particles in the collection media is straightforward. Reliable techniques have been developed for the extraction of these particles from aerogel. Coordinated analyses are also relatively straightforward, often beginning with synchrotron-based x-ray fluorescence (S-XRF), X-ray Absorption Near-Edge Spectoscopy (XANES) and x-ray diffraction (S-XRD) analyses of particles while still embedded in small extracted wedges of aerogel called ``keystones'', followed by ultramicrotomy and TEM, Scanning Transmission X-ray Microscopy (STXM) and ion microprobe analyses (e.g., Ogliore et al., 2010). Impacts in foils can be readily analyzed by SEM-EDX, and TEM analysis after FIB liftout sample preparation. In contrast, the interstellar dust collection is vastly more challenging. The sample size is approximately six orders of magnitude smaller in total mass. The largest particles are only a few pg in mass, of which there may be only approx.10 in the entire collection. The technical challenges, however, are matched by the scientific importance of the collection. We formed a consortium carry out the Stardust Interstellar Preliminary Examination (ISPE) to carry out an assessment of this collection, partly in order to characterize the collection in sufficient detail so that future investigators could make well-informed sample requests. The ISPE is the sixth PE on extraterrestrial collections carried out with NASA support. Some of the basic questions that we asked were: how many impacts are there in the collector, and what fraction of them have characteristics consistent with extraterrestrial materials? What is the elemental composition of the rock-forming elements? Is there crystalline material? Are there organics? Here we present coordinated microanalyses of particles captured in aerogel, using S-FTIR, S-XRF, STXM, S-XRD; and coordinated microanalyses of residues in aluminum foil, using SEMEDX, Auger spectroscopy, STEM, and ion microprobe. We discuss a novel approach that we employed for identification of tracks in aerogel, and new sample preparation techniques developed during the ISPE. We have identified seven particles - three in aerogel and four in foils - that are most consistent with an interstellar origin. The seven particles exhibit a large diversity in elemental composition. Dynamical evidence, supported supported by laboratory simulations of interstellar dust impacts in aerogel and foils, and numerical modeling of interstellar dust propagation in the heliosphere, suggests that at least some of the particles have high optical cross-section, perhaps due to an aggregate structure. However, the observations are most consistent with a variety of morphologies

The Astrobiology Space Infrared Explorer (ASPIRE) is a Probe-class mission concept developed as part of NASA's Astrophysics Strategic Mission Concept studies. 1 2 ASPIRE uses infrared spectroscopy to explore the identity, abundance, and distribution of molecules, particularly those of astrobiological importance throughout the Universe. ASPIRE's observational program is focused on investigating the evolution of ices and organics in all phases of the lifecycle of carbon in the universe, from stellar birth through stellar death while also addressing the role of silicates and gas-phase materials in interstellar organic chemistry. ASPIRE achieves these goals using a Spitzer-derived, cryogenically-cooled, 1-m-class telescope in an Earth drift-away heliocentric orbit, armed with a suite of infrared spectrometers operating in the 2.5–36 micron wavelength region supported by a Kepler-based spacecraft bus. This paper summarizes the results of the ASPIRE Origins Probe Mission Concept Study while focusing on its high heritage mission implementation.

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.

On 6 October 2008, a small Earth-bound asteroid designated 2008 TC3 was discovered by the Catalina Sky Survey. Some 19 hours — and many astronomical observations — later it entered the atmosphere and disintegrated at 37 km altitude. No macroscopic fragments were expected to have survived but a dedicated search along the approach trajectory in a desert in northern Sudan has recovered 47 meteorites, fragments of a single body named Almahata Sitta, with a total mass of 3.95 kg. The asteroid and meteorite reflectance spectra identify the asteroid as surface matter from a class 'F' asteroid, material so fragile that it was not previously represented in meteorite collections. To have recovered meteorites from a known class of asteroids is a coup on a par with a successful spacecraft sample-return mission — without the rocket science. On 6 October 2008, a small asteroid designated 2008 TC3 hit the Earth in northern Sudan. Jenniskens et al. searched along the approach trajectory and luckily found 47 bits of a meteorite named Almahata Sitta. Analysis reveals it to be a porous achondrite and a polymict ureilite, and so the asteroid was F-class (dark carbon-rich anomalous ureilites). In the absence of a firm link between individual meteorites and their asteroidal parent bodies, asteroids are typically characterized only by their light reflection properties, and grouped accordingly into classes1,2,3. On 6 October 2008, a small asteroid was discovered with a flat reflectance spectrum in the 554–995 nm wavelength range, and designated 2008 TC3 (refs 4–6). It subsequently hit the Earth. Because it exploded at 37 km altitude, no macroscopic fragments were expected to survive. Here we report that a dedicated search along the approach trajectory recovered 47 meteorites, fragments of a single body named Almahata Sitta, with a total mass of 3.95 kg. Analysis of one of these meteorites shows it to be an achondrite, a polymict ureilite, anomalous in its class: ultra-fine-grained and porous, with large carbonaceous grains. The combined asteroid and meteorite reflectance spectra identify the asteroid as F class3, now firmly linked to dark carbon-rich anomalous ureilites, a material so fragile it was not previously represented in meteorite collections.

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.

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N2-, CH4-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N2, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ~ 0.9 and O/C ~ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.