The organic composition of Comet C/2000 WM1 (LINEAR) revealed through infrared spectroscopy

We investigated the parent volatile composition of the Oort cloud Comet C/2000 WM₁ (LINEAR) on 23-25 November 2001, using the Near Infrared Echelle Spectrograph on the Keck II telescope. Flux-calibrated spectra, absolute production rates, and mixing ratios are presented for H₂O, HCN, CH₄, C₂H₂, C₂H₆, H₂CO, CH₃OH and CO. Compared with “organics-normal” comets, WM₁ is moderately depleted in HCN, CH₄ and CH₃OH, and is even more depleted in C₂H₂ and CO. Its composition is thus intermediate to comets that are severely depleted in their organic volatile composition and those that exhibit “normal” organic volatile abundances. We argue that WM₁ may have formed closer to the young Sun than “organics-normal” comets, but at greater distance than the severely depleted comets, before its ejection to the Oort cloud. The mixing ratios of the above-listed organic volatiles agree day-by-day for 23-25 November 2001. Thus, there is no evidence of macroscopic heterogeneity in chemistry of this comet’s nucleus at the achieved measurement accuracy. As the first comet to show moderate organic depletion in parent volatiles, WM₁ represents an important addition to the emerging taxonomic classification based on chemical composition.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Infrared measurements of the chemical composition of C/2006 P1 McNaught

C/2006 P1 McNaught is a dynamically new comet from the Oort cloud that passed very close to the Sun, driving overall volatile production rates up to about 10³¹ molecules s⁻¹. Post-perihelion observations were obtained in a target-of-opportunity campaign using the CSHELL instrument at the NASA Infrared Telescope Facility atop Mauna Kea, Hawaii, on UT 2007 January 27 and 28. Eight parent volatiles (H₂O, CH₄, C₂H₂, C₂H₆, HCN, CO, NH₃, H₂CO) and two daughter fragments (OH and NH₂) were detected, enabling the determination of a rotational temperature and production rate for H₂O on UT January 27 and absolute and relative production rates for all the detected parent species on UT January 28. The chemical composition measured in the coma suggests that this close perihelion passage stripped off processed outer surface layers, likely exposing relatively fresh primordial material during these observations. The post-perihelion abundances we measure for CO and CH₄ (relative to H₂O) are slightly depleted while C₂H₂, NH₂ and possibly NH₃ are enhanced when compared to the overall comet population. Measured abundances for other detected molecular species were within the range typically observed in comets.     

Extreme Ultraviolet Photon-Induced Chemical Reactions in the C2H2-H2O Mixed Ices at 10 K

Experimental results on the spectral identification of new infrared absorption features and the changes of their absorbances produced through vacuum ultraviolet-extreme ultraviolet (VUV-EUV) photon-induced chemical reactions in the C₂H₂-H₂O mixed ices at 10 K are obtained. To the best of our knowledge, this is the first time that EUV photons have been employed in the study of the photolysis of ice analogues. Two different compositions, i.e., C₂H₂:H₂O=1:4 and 1:1, were investigated in this work. A tunable intense synchrotron radiation light source available at the Synchrotron Radiation Research Center, Hsinchu, Taiwan, was employed to provide the required VUV-EUV photons. In this study, the photon wavelengths selected to irradiate the icy samples corresponded to the prominent solar hydrogen, helium, and helium ion lines at 121.6 nm, 58.4 nm, and 30.4 nm, respectively. The photon dosages used were typically in the range of 1×10¹⁵ to 2×10¹⁷ photons. Molecular species produced and identified in the ice samples at 10 K resulting from VUV-EUV photon irradiation are mainly CO, CO₂, CH₄, C₂H₆, CH₃OH, and H₂CO. In addition to several unidentified features, we have tentatively assigned several absorption features to HCO, C₃H₈, and C₂H₅OH. While new molecular species were formed, the original reactants, i.e., H₂O and C₂H₂, were detectably depleted due to their conversion to other species. The new chemical species produced by irradiation of photons at 30.4 nm and 58.4 nm can be different from those produced by the 121.6-nm photolysis. In general, the product column density of CO reaches saturation at a lower photon dosage than that of CO₂. Furthermore, the production yield of CO is higher than that of CO₂ in the photon irradiation. In the present study, we also observe that the photon-induced chemical reaction yields are high using photons at 30.4 and 58.4 nm. The results presented in this work are essential to our understanding of chemical synthesis in ice analogues, e.g., the cometary-type ices and icy satellites of planetary systems.     

Methane in Oort cloud comets

We detected CH₄ in eight Oort cloud comets using high-dispersion (λ/Δλ∼2×10⁴) infrared spectra acquired with CSHELL at NASA's IRTF and NIRSPEC at the W.M. Keck Observatory. The observed comets were C/1995 O1 (Hale-Bopp), C/1996 B2 (Hyakutake), C/1999 H1 (Lee), C/1999 T1 (McNaught-Hartley), C/1999 S4 (LINEAR), C/2000 WM₁ (LINEAR), C/2001 A2 (LINEAR), and 153/P Ikeya-Zhang (C/2002 C1). We detected the R0 and R1 lines of the ν₃ vibrational band of CH₄ near 3.3 μm in each comet, with the exception of McNaught-Hartley where only the R0 line was measured. In order to obtain production rates, a fluorescence model has been developed for this band of CH₄. We report g-factors for the R0 and R1 transitions at several rotational temperatures typically found in comet comae and relevant to our observations. Using g-factors appropriate to T_rot as determined from HCN, CO and/or H₂O and C₂H₆, CH₄ production rates and mixing ratios are presented. Abundances of CH₄/H₂O are compared among our existing sample of comets, in the context of establishing their place of origin. In addition, CH₄ is compared to native CO, another hypervolatile species, and no correlation is found among the comets observed.     

Spectroscopy of Comet Hale-Bopp in the infrared

High resolution infrared spectra of Comet C/1995 O1 (Hale-Bopp) were obtained during 2-5 March 1997 UT from the NASA Infrared Telescope Facility on Mauna Kea, Hawaii, when the comet was at r≈1.0 AU from the Sun pre-perihelion. Emission lines of CH₄, C₂H₆, HCN, C₂H₂, CH₃OH, H₂O, CO, and OH were detected. The rotational temperature of CH₄ in the inner coma was T_rot=110±20 K. Spatial profiles of CH₄, C₂H₆, and H₂O were consistent with release solely from the nucleus. The centroid of the CO emission was offset from that of the dust continuum and H₂O. Spatial profiles of the CO lines were much broader than those of the other molecules and asymmetric. We estimate the CO production rate using a simplified outflow model: constant, symmetric outflow from the peak position. A model of the excitation of CO that includes optical depth effects using an escape probability method is presented. Optical depth effects are not sufficient to explain the broad spatial extent. Using a parent+extended-source model, the broad extent of the CO lines can be explained by CO being produced mostly (∼90% on 5 March) from an extended source in the coma. The CO rotational temperature was near 100 K. Abundances relative to H₂O (in percent) were 1.1±0.3 (CH₄), 0.39±0.10 (C₂H₆), 0.18±0.04 (HCN), 0.17±0.04 (C₂H₂), 1.7±0.5 (CH₃OH), and 37-41 (CO, parent+extended source). These are roughly comparable to those obtained for other long-period comets also observed in the infrared, though CO appears to vary.     

Reflectance and transmittance spectra (2.2-2.4 μm) of ion irradiated frozen methanol

We present near-IR (2.2-2.4 μm) reflectance and transmittance spectra of frozen (16 and 77 K) methanol (CH₃OH) and water-methanol (1:1) mixtures before and after irradiation with 30 keV He⁺ and 200 keV H⁺ ions. Spectra of other simple hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆) and CO have also been obtained both to help in the identification of the new molecules formed after ion irradiation of methanol-rich ices, and to get insight into the question of the presence of simple frozen hydrocarbons on the surface of some objects in the outer Solar System. The results confirm what obtained by studies performed in different spectral ranges, namely the ion-induced formation of CO and CH₄, and, for the first time, evidence a strong decrease of the intensity of the methanol band at about 2.34 μm in comparison with that at 2.27 μm. The results are discussed in view of their relevance for icy objects in the Solar System (namely comets, Centaurs, and Kuiper belt objects) where CH₃OH has been observed or suggested to be present.     

CO/CO2 Molecular Number Ratio Produced by ion Irradiation of Ices

We have quantitatively studied, by infrared absorption spectroscopy, the CO/CO₂ molecular number ratio after ion irradiation of ices and mixtures containing astrophysically relevant species such as CO, CO₂, H₂O, CH₄, CH₃OH, NH₃, O₂, and N₂ at 12–15 K. The ratios have also been measured after warm up to temperatures between 12 and 200 K. As a general result we find that the CO/CO₂ ratio decreases with the irradiation dose (amount of energy deposited on the sample). In all of the studied mixtures, as expected, it decreases with increasing temperature because of CO sublimation. However the temperature where CO sublimes strongly depends on the initial mixture, remaining at a temperature over 100 K in some cases. Our results might be relevant to interpret the observed CO/CO₂ ratio in several astrophysical scenarios such as planetary icy surfaces and ice mantles on grains in the interstellar medium. This revised version was published online in July 2006 with corrections to the Cover Date.     

Monte Carlo modeling of neutral gas and dust in the coma of Comet 1P/Halley

The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer and the Dust Impact Detection System onboard the Giotto spacecraft taken during the fly-by at Comet 1P/Halley in 1986. We also show that our model is in good agreement with contemporaneous measurements obtained by the International Ultraviolet Explorer, sounding rocket experiments, and various ground based observations.The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique (Tenishev, V., Combi, M., Davidsson, B. [2008]. Astrophys. J. 685, 659-677) by tracking trajectories of gas molecules and dust grains under the influence of the comet’s weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H₂O, CO, H₂CO, CO₂, CH₃OH, C₂H₆, C₂H₄, C₂H₂, HCN, NH₃, and CH₄) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H₂, O, OH, C, CH, CH₂, CH₃, N, NH, NH₂, C₂, C₂H, C₂H₅, CN, and HCO) from the comet’s surface all the way out to 10⁶ km.As a result we are able to further constrain cometary the gas production rates of CO (13%), CO₂ (2.5%), and H₂CO (1.5%) relative to water without invoking unknown extended sources.     

A multi-wavelength study of parent volatile abundances in Comet C/2006 M4 (SWAN)

Volatile organic emissions were detected post-perihelion in the long-period Comet C/2006 M4 (SWAN) in October and November 2006. Our study combines target-of-opportunity infrared observations using the Cryogenic Echelle Spectrometer (CSHELL) at the NASA-IRTF 3-m telescope, and millimeter wavelength observations using the Arizona Radio Observatory (ARO) 12-m telescope. Five parent volatiles were measured with CSHELL (H₂O, CO, CH₃OH, CH₄, and C₂H₆), and two additional species (HCN and CS) were measured with the ARO 12-m. These revealed highly depleted CO and somewhat enriched CH₃OH compared with abundances observed in the dominant group of long-period (Oort cloud) comets in our sample and similar to those observed recently in Comet 8P/Tuttle. This may indicate highly efficient H-atom addition to CO at very low temperature (∼10-20 K) on the surfaces of interstellar (pre-cometary) grains. Comet C/2006 M4 had nearly “normal” C₂H₆ and CH₄, suggesting a processing history similar to that experienced by the dominant group. When compared with estimated water production at the time of the millimeter observations, HCN was slightly depleted compared with the normal abundance in comets based on IR observations but was consistent with the majority of values from the millimeter. The ratio CS/HCN in C/2006 M4 was within the range measured in ten comets at millimeter wavelengths. The higher apparent H-atom conversion efficiency compared with most comets may indicate that the icy grains incorporated into C/2006 M4 were exposed to higher H-atom densities, or alternatively to similar densities but for a longer period of time.     

The molecular composition of Comet C/2007 W1 (Boattini): Evidence of a peculiar outgassing and a rich chemistry

We measured the chemical composition of Comet C/2007 W1 (Boattini) using the long-slit echelle grating spectrograph at Keck-2 (NIRSPEC) on 2008 July 9 and 10. We sampled 11 volatile species (H₂O, OH^∗, C₂H₆, CH₃OH, H₂CO, CH₄, HCN, C₂H₂, NH₃, NH₂, and CO), and retrieved three important cosmogonic indicators: the ortho-para ratios of H₂O and CH₄, and an upper-limit for the D/H ratio in water. The abundance ratios of almost all trace volatiles (relative to water) are among the highest ever observed in a comet. The comet also revealed a complex outgassing pattern, with some volatiles (the polar species H₂O and CH₃OH) presenting very asymmetric spatial profiles (extended in the anti-sunward hemisphere), while others (e.g., C₂H₆ and HCN) showed particularly symmetric profiles. We present emission profiles measured along the Sun-comet line for all observed volatiles, and discuss different production scenarios needed to explain them. We interpret the emission profiles in terms of release from two distinct moieties of ice, the first being clumps of mixed ice and dust released from the nucleus into the sunward hemisphere. The second moiety considered is very small grains of nearly pure polar ice (water and methanol, without dark material or apolar volatiles). Such grains would sublimate only very slowly, and could be swept into the anti-sunward hemisphere by radiation pressure and solar-actuated non-gravitational jet forces, thus providing an extended source in the anti-sunward hemisphere.     

The organic composition of Comet C/2001 A2 (LINEAR): I. Evidence for an unusual organic chemistry

We used the NIRSPEC instrument on the Keck-2 telescope atop Mauna Kea, HI to observe Comet C/2001 A2 (LINEAR) in a Target of Opportunity campaign on UT 2001 July 9.5, 10.5 August 4.4, 10.5. We measured seven organic parent volatiles (C₂H₆, C₂H₂, HCN, CH₄, CO, CH₃OH, H₂CO) simultaneously with H₂O. We obtained absolute production rates and relative abundances for parent volatiles, and also measured rotational temperatures for several of these species. The chemical composition of C/2001 A2 differs substantially from any comet we have observed to date. The abundances we measure (relative to H₂O) for C₂H₆, C₂H₂, HCN, and CH₃OH are enriched by a factor of ∼2 to 3 in C/2001 A2 compared with most comets in our database. Other molecular species were detected within the typical range of measured abundances. C/2001 A2 presented a unique opportunity to study the chemistry of a fragmenting comet where pristine areas are exposed to the Sun.     

Chemical Composition Diversity Among 24 Comets Observed At Radio Wavelengths

We present a comparative study on molecular abundances in comets basedon millimetre/submillimetre observations made with the IRAM 30-m,JCMT, CSO and SEST telescopes. This study concerns a sample of 24comets (6 Jupiter-family, 3 Halley-family, 15 long-period) observedfrom 1986 to 2001 and 8 molecular species (HCN, HNC, CH₃CN,CH₃OH, H₂CO, CO, CS, H₂S). HCN was detected in all comets,while at least 2 molecules were detected in 19 comets. From the sub-sample of comets for which contemporary H₂O productionrates are available, we infer that the HCN abundance relative to water variesfrom 0.08% to 0.25%. With respect to other species, HCN is the moleculewhich exhibits the lowest abundance variation from comet to comet. Therefore,production rates relative to that of HCN can be used for a comparative study ofmolecular abundances in the 19 comets. It is found that: CH₃OH/HCN varies from ≤ 9 to 64; CO/HCN varies from ≤ 24 to 180; H₂CO/HCN varies between 1.6 and 10; and H₂S/HCN varies between 1.5 and 7.6. This study does not show any clear correlation between the relative abundancesand the dynamical origins of the comets, or their dust-to-gas ratios.     

A theoretical study of Comet Halley's spectrum in the infrared range

Synthetic spectra of Comet Halley between 2.5 and 15 μm are calculated on the basis of current cometary models. This study shows that molecules which are most likely detectable in the infrared range include H₂O, CO, CO₂, CH₄, NH₃, N₂H₄, and H₂CO. The flux emitted by these molecules, mostly due to resonant scattering, should be sufficient for detection by a flyby mission.     

The structure of cometary atmospheres

The temperature distributions in cometary atmospheres at various heliocentric distances for comets of Bennett and Encke types have been calculated by taking into account heating due to the absorption of solar ultraviolet radiation, cooling by H₂O far infrared emission, and various dynamical processes (expansion, advection, and thermal conduction). The agreement of the results with the observations is in general satisfactory. The conversion of CH₄ and NH₃ to CO and N₂ through thermochemical reaction with H₂O is concluded to be impossible, since the temperature is too low at a heliocentric distance 1.5 AU where CO⁺ ions begin to be observable.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Near-infrared laboratory spectra of solid H2O/CO2 and CH3OH/CO2 ice mixtures

We present near-IR spectra of solid CO₂ in H₂O and CH₃OH, and find they are significantly different from that of pure solid CO₂. Peaks not present in either pure H₂O or pure CO₂ spectra become evident when the two are mixed. First, the putative theoretically forbidden CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹), that is absent from our spectrum of pure solid CO₂, is prominent in the spectra of H₂O/CO₂=5 and 25 mixtures. Second, a 2.74-μm (3650 cm⁻¹) dangling OH feature of H₂O (and a potentially related peak at 1.89 μm) appear in the spectra of CO₂-H₂O ice mixtures, but are probably not diagnostic of the presence of CO₂. Other CO₂ peaks display shifts in position and increased width because of intermolecular interactions with H₂O. Warming causes some peak positions and profiles in the spectrum of a H₂O/CO₂=5 mixture to take on the appearance of pure CO₂. Absolute strengths for absorptions of CO₂ in solid H₂O are estimated. Similar results are observed for CO₂ in solid CH₃OH. Since the CO₂ (2ν₃) overtone near 2.134 μm (4685 cm⁻¹) is not present in pure CO₂ but prominent in mixtures, it may be a good observational (spectral) indicator of whether solid CO₂ is a pure material or intimately mixed with other molecules. These observations may be applicable to Mars polar caps as well as outer Solar System bodies.     

Near-infrared spectral monitoring of Triton with IRTF/SpeX II: Spatial distribution and evolution of ices

This report arises from an ongoing program to monitor Neptune’s largest moon Triton spectroscopically in the 0.8 to 2.4 μm range using IRTF/SpeX. Our objective is to search for changes on Triton’s surface as witnessed by changes in the infrared absorption bands of its surface ices N₂,CH₄,H₂O, CO, and CO₂. We have recorded infrared spectra of Triton on 53 nights over the ten apparitions from 2000 to 2009. The data generally confirm our previously reported diurnal spectral variations of the ice absorption bands (Grundy and Young, 2004). Nitrogen ice shows a large amplitude variation, with much stronger absorption on Triton’s Neptune-facing hemisphere. We present evidence for seasonal evolution of Triton’s N₂ ice: the 2.15 μm absorption band appears to be diminishing, especially on the Neptune-facing hemisphere. Although it is mostly dissolved in N₂ ice, Triton’s CH₄ ice shows a very different longitudinal variation from the N₂ ice, challenging assumptions of how the two ices behave. Unlike Triton’s CH₄ ice, the CO ice does exhibit longitudinal variation very similar to the N₂ ice, implying that CO and N₂ condense and sublimate together, maintaining a consistent mixing ratio. Absorptions by H₂O and CO₂ ices show negligible variation as Triton rotates, implying very uniform and/or high latitude spatial distributions for those two non-volatile ices.     

Models of the cometary coma in which abundances are calculated for various heliocentric distances

One-dimensional radial models of the chemistry in cometary comae have been constructed for heliocentric distances ranging from 2 to 0.125 AU. The coma's opacity to solar radiation is included and photolytic reaction rates are calculated. A parent volatile mixture similar to that found in interstellar molecular clouds is assumed. Profiles through the coma of number density and column density are presented for H₂O, OH, O, CN, C₂, C₃, CH, and NH₂. Whole-coma abundances are presented for NH₂, CH, C₂, C₃, CN, OH, CO⁺, H₂O⁺, CH⁺, N₂⁺, and CO₂⁺.     

Infrared study of ion-irradiated N2-dominated ices relevant to Triton and Pluto: formation of HCN and HNC

Infrared spectra and radiation chemical behavior of N₂-dominated ices relevant to the surfaces of Triton and Pluto are presented. This is the first systematic IR study of proton-irradiated N₂-rich ices containing CH₄ and CO. Experiments at 12 K show that HCN, HNC, and diazomethane (CH₂N₂) form in the solid phase, along with several radicals. NH₃ is also identified in irradiated N₂ + CH₄ and N₂ + CH₄ + CO. We show that HCN and HNC are made in irradiated binary ice mixtures having initial N₂/CH₄ ratios from 100 to 4, and in three-component mixtures have an initial N₂/(CH₄ + CO) ratio of 50. HCN and HNC are not detected in N₂-dominated ices when CH₄ is replaced with C₂H₆, C₂H₂, or CH₃OH.The intrinsic band strengths of HCN and HNC are measured and used to calculate G(HCN) and G(HNC) in irradiated N₂ + CH₄ and N₂ + CH₄ + CO ices. In addition, the HNC/HCN ratio is calculated to be ∼1 in both icy mixtures. These radiolysis results reveal, for the first time, solid-phase synthesis of both HCN and HNC in N₂-rich ices containing CH₄.We examine the evolution of spectral features due to acid-base reactions (acids such as HCN, HNC, and HNCO and a base, NH₃) triggered by warming irradiated ices from 12 K to 30-35 K. We identify anions (OCN⁻, CN⁻, and N3−) in ices warmed to 35 K. These ions are expected to form and survive on the surfaces of Triton and Pluto. Our results have astrobiological implications since many of these products (HCN, HNC, HNCO, NH₃, NH₄OCN, and NH₄CN) are involved in the syntheses of biomolecules such as amino acids and polypeptides.