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Formaldehyde in envelopes of interstellar dark clouds

Observed formaldehyde column densities of 1 x 10 to the 12th - 3 x 10 to the 13th/sq cm in cloud envelopes along lines of sight with A(V) = 1-4 mag can not be explained with the current understanding of interstellar gas phase chemistry. However, these column densities can be reproduced by a simple time-dependent model in which H2CO is supplied to the gas phase by the erosion of icy grain mantles. The release of H2CO from the grain mantles must occur on time scales comparable to the time scales for mixing from the cloud interior to the cloud envelope. Thus, in low-density regions of clouds, it appears that formaldehyde is the second molecule whose gas phase source is primarily ejection from grains. This simple model suggests understanding gas phase steady state in clouds on macroscopic, rather than microscopic, spatial scales.

Federman, S. R.↗

Observations of formaldehyde and search for cyanoacetylene in Comet Brorsen-Metcalf (1989o)

The Very Large Array (VLA) was used in September 1989 to search Comet P/Brorsen-Metcalf (1989o) for the 1 sub 11-1 sub 10 transition of formaldehyde (H2CO) at 4,829.659 MHz and for the J equals 1-0, F equals 2-1 rotational transition of cyanoacetylene (HC3N) at 9098.3321 MHz. A new technique was used in reducing the data. Data blocks which were either 3x3 pixels, 5x5 pixels, or 9x9 pixels were examined for a signal from H2CO. Using this approach, different pixel clusters within the field of view can be sampled to optimize the coupling of the synthesized beam to the gas distribution. HC3N is of immediate interest as a cometary molecule because it may be a reservoir of carbon and a source of cometary CN. Our search for HC3N emission at 3.3 cm wavelength demonstrated that for this molecule the VLA can be expected to reach significant levels of sensitivity in many comets.

Snyder, Lewis E.↗

An infrared search for formaldehyde in several comets

Models which assume either a parent or a distributed source for H2CO are presently used to retrieve 3-sigma upper limits to that species' production rate from a 3.55-3.64 micron search for cometary IR emission from the nu1 and nu5 bands of formaldehyde. A parent-source H2CO production rate relative to water of 0.15-0.80 percent is obtained, together with a distributed source production rate of 1.7-5.8 percent.

Reuter, Dennis C.↗

Formaldehyde reactions in dark clouds

The low-pressure reactions of formaldehyde (H2CO) with D(+), D2(+), D3(+), and He(+) are studied by the ion-cyclotron resonance technique. These reactions are potential loss processes for formaldehyde in cores of dark interstellar clouds. The deuterated reactants represent direct analogs for protons. Rate coefficients and branching ratios of product channels have been measured. Charge transfer is observed to be the dominant reaction of H2CO with D(+), D2(+), and He(+) ions. Only the D3(+) reaction exhibits a proton-transfer channel. All reactions proceed at rate coefficients near the collision limit. Proton-deuteron exchange reactions are found to be inefficient processes in the formaldehyde system.

Sen, A. D.↗

Computed potential energy surfaces for chemical reactions

The work on the NH + NO system which was described in the last progress report was written up and a draft of the manuscript is included in the appendix. The appendix also contains a draft of a manuscript on an Ar + H + H surface. New work which was completed in the last six months includes the following: (1) calculations on the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels in the CH3 + OH reaction; (2) calculations for the NH2 + O reaction; (3) calculations for the CH3 + O2 reaction; and (4) calculations for CH3O and the two decomposition channels--CH2OH and H + H2CO. Detailed descriptions of this work will be given in manuscripts; however, brief descriptions of the CH3 + OH and CH3 + O2 projects are given.

Heinemann, K.↗

Organic Molecules in Oxygen-Rich Circumstellar Envelopes: Methanol and Hydrocarbons

The existence of anomalously high abundances of gaseous CH4 has been invoked to explain the unexpectedly high abundances of the carbon-bearing molecules HCN and H2CO in the outflows from O-rich red giants. We have modelled the chemistry that proceeds in the outer envelope when CH4 is injected from the inner envelope. We find that photolysis by the interstellar radiation field drives an ion-neutral chemistry which produces several organic molecules. The calculated abundances of CH3OH, C2H and C2 can be comparable to those calculated for H2CO and HCN. Species such as C2H4, C2H2 and CH3CN can also be abundant. A search for CH3OH and C2H in several O-rich outflows known to exhibit strong HCN emission is needed. As it derives entirely from the CH4 photochain, is insensitive to the envelope temperature distribution, and has accessible transitions at millimetre wavelengths, the detection of the C2H radical would provide further indirect support for the presence of the hypothesized methane.

Charnley, S. B.↗

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.↗

Evolution of Interstellar Grains

During the past two decades observations combined with laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in large molecular clouds where simple molecules are formed by dust-grain and gas-phase reactions. Gaseous species striking the cold (10K) dust stick, forming an icy grain mantle. This accretion, coupled with UV photolysis, produces a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species. The evidence for these compounds, as well as carbon-rich materials, will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk . The second part of the presentation will focus on interstellar/precometary ice photochemical evolution and the species likely to be found in comets. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs will be discussed. Ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. When ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C=N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature an organic residue remains. This is composed primarily of hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene-related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating unrealistic interstellar ice analogs or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures.

Allamandola, Lou J.↗

Development of an automated diode-laser-based multicomponent gas sensor

The implementation and application of a portable fiber-coupled trace-gas sensor for the detection of several trace gases, including CO2, CH4, and H2CO, are reported. This particular sensor is based on a cw fiber-amplified near-infrared (distributed Bragg reflector) diode laser and an external cavity diode laser that are frequency converted in a periodically poled lithium niobate crystal to the mid-IR spectroscopic fingerprint region (3.3-4.4 micrometers). A continuous absorption spectrum of CH4 and H2CO from 3.37 to 3.10 micrometers with a spectral resolution of 40 MHz (approximately 0.0013 cm-1) demonstrated the spectral performance that can be achieved by means of automated wavelength tuning and phase matching with stepper motor control. Autonomous long-term detection of ambient CO2 and CH4 over a 3- and 7-day period was also demonstrated.

NASA Discipline Environmental Health↗

Complex Cometary Phenomena: The Distributed Source

Observations of H2CO toward comet Hale-Bopp demonstrate that this molecule has an extended distribution, which cannot be explained by direct sublimation from the nucleus or gas phase processes in the coma. A likely source of 142CO in comets may be coma grains composed of an organic-dominated silicate-organic matrix. These grains are released from the nucleus and are vaporized or thermally degraded by solar heating, ejecting organic molecules into the expanding coma. Hence, organic molecules with short photodissociation lifetimes (<10(exp 4) km) such as H2CO can be found much farther from the comet nucleus than their photodestruction rates would suggest. Distributed sources are also considered for other species such as CO, CN, and CS. We will present an overview of observations and experiments that can help decipher the origin of such species.

Milam, Stefanie N.↗

Centimeter, Millimeter, and Submillimeter Observations of Comet l03P/Hartley 2

The close approach (0.12 AU) of Comet 103P/Hartley 2 to the Earth only 8 days prior to perihelion provided a unique opportunity to probe the chemical composition of this object. Additionally, supporting data was acquired during the EPOXI (Extrasolar Planet Observation and Deep Impact Extended Investigation) flyby mission [1], which provided high resolution infrared spectra and images. Observations were conducted from four facilities, contributing to the large ground-based consortium organized in support of the EPOXI mission [2]. The Arizona Radio Observatory's 12m telescope, Kitt Peak, AZ, and Submillimeter telescope, Mt. Graham, AZ, as well as the James Clerk Maxwell Telescope, Mauna Kea, HI and the Greenbank 100m telescope, Greenbank, WV, were employed for this study covering 20 cm, 3 cm, and 0.8-3 mm. Data were obtained, collectively, from 12 October 2010 to 5 November 2010 [3]. HCN, CH3OH, H2CO, HNC, OH, and CS were detected, and upper limits on the abundance of H2S, SO2, c-C3H2, and deuterated isotopologues of HCN, H2CO, and H2O were measured. Upper limits on the D/H ratio derived from DCN gave D/H less than 0.01[3]. Detailed analysis of these data will help constrain the temperature, abundances, variance or periodicity of a given species, and can be compared to results from other comets, as well as support the data obtained from the EPOXI mission. The full analysis and comparison will be presented.

Milam, Stefanie N.↗

The Composition of Comet C/2009 P1 (Garradd) from Infrared Spectroscopy: Evidence for an Oxygen-Rich Heritage?

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which their ices are modified remains a key question in cometary science. One way to address this is to measure the relative abundances of primary (parent) volatiles in comets (i.e., those ices native to the nucleus). High-resolution (lambda/delta lambda greater than 10(exp 4)) infrared spectroscopy is a powerful tool for measuring parent volatiles in comets through their vibrational emissions in the approximately 3-5 micrometer region. With modern instrumentation on world-class telescopes, we can quantify a multitude of species (e.g., H2O, C2H2, CH4, C2H6, CO, H2CO, CH3OH, HCN, NH3), even in comets with modest gas production. In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6, and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules and their variability among comets contributes to understanding the synthesis of the more complex prebiotic compounds.

DiSanti, M. A.↗

The Composition of Comet C/2009 PI (Garradd) from Infrared Spectroscopy: Evidence for an Oxygen-Rich Heritage?

Comets retain relatively primitive icy material remaining from the epoch of Solar System for111ation, however the extent to which their ices are modified remains a key question in cometary science. One way to address this is to measure the relative abundances of primary (parent) volatiles in comets (i.e., those ices native to the nucleus). High-resolution (lambda/delta lambda greater than 10(exp 4)) infrared spectroscopy is a powerful tool for measuring parent volatiles in comets through their vibrational emissions in the ~ 3-5 micrometer region. With modern instrumentation on worldclass telescopes, we can quantify a multitude of species (e.g., H2O, C2H2, CH4, C2H6 CO, H2CO, CH3OH, HCN, NH3), even in comets with modest gas production. In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules and their variability among comets contributes to understanding the synthesis of the more complex prebiotic compounds.

DiSanti, M. A.↗

Observations of Carbon Isotopic Fractionation in Interstellar Formaldehyde

Primitive Solar System materials (e.g. chondrites. IDPs, the Stardust sample) show large variations in isotopic composition of the major volatiles (H, C, N, and O ) even within samples, witnessing to various degrees of processing in the protosolar nebula. For ex~ ample. the very pronounced D enhancements observed in IDPs [I] . are only generated in the cold. dense component of the interstellar medium (ISM), or protoplanetary disks, through ion-molecule reactions in the presence of interstellar dust. If this isotopic anomaly has an interstellar origin, this leaves open the possibility for preservation of other isotopic signatures throughout the form ation of the Solar System. The most common form of carbon in the ISM is CO molecules, and there are two potential sources of C-13 fractionation in this reservoir: low temperature chemistry and selective photodissociation. While gas-phase chemistry in cold interstellar clouds preferentially incorporates C-13 into CO [2], the effect of self-shielding in the presence of UV radiation instead leads to a relative enhancement of the more abundant isotopologue, 12CO. Solar System organic material exhibit rather small fluctuations in delta C-13 as compared to delta N-15 and delta D [3][1], the reason for which is still unclear. However, the fact that both C-13 depleted and enhanced material exists could indicate an interstellar origin where the two fractionation processes have both played a part. Formaldehyde (H2CO) is observed in the gas-phase in a wide range of interstellar environments, as well as in cometary comae. It is proposed as an important reactant in the formation of more complex organic molecules in the heated environments around young stars, and formaldehyde polymers have been suggested as the common origin of chondritic insoluable organic matter (IOM) and cometary refractory organic solids [4]. The relatively high gas-phase abundance of H2CO observed in molecular clouds (10(exp- 9) - 10(exp- 8) relative to H2) makes it feasible to observe its less common isotopologues. As a step in our investigation of C-13 fractionation patterns in the ISM, we here present comparisons between observations of the C-13 fraction in formaldehyde, and chemical fractionation models.

Wirstrom, E. S.↗

High-Resolution Infrared Spectroscopic Measurements of Comet 2PlEncke: Unusual Organic Composition and Low Rotational Temperatures

We present high-resolution infrared spectroscopic measurements of the ecliptic comet 2P/Encke, observed on 4-6 Nov. 2003 during its close approach to the Earth, using the Near Infrared Echelle Spectrograph on the Keck II telescope. We present flux-calibrated spectra, production rates, and mixing ratios for H2O, CH3OH, HCN, H2CO, C2H2, C2H6, CH4 and CO. Comet 2P/Encke is a dynamical end-member among comets because of its short period of 3.3 years. Relative to "organics-normal" comets, we determined that 2PlEncke is depleted in HCN, H2CO, C2H2, C2H6, CH4 and CO, but it is enriched in CH3OH. We compared mixing ratios of these organic species measured on separate dates, and we see no evidence of macroscopic chemical heterogeneity in the nucleus of 2P/Encke, however, this conclusion is limited by sparse temporal sampling. The depleted abundances of most measured species suggest that 2P/Encke may have formed closer to the young Sun, before its insertion to the Kuiper belt, compared with "organics-normal" comets - as was previously suggested for other depleted comets (e.g. C/1999 S4 (LINEAR)). We measured very low rotational temperatures of 20 - 30 K for H2O, CH3OH and HCN in the near nucleus region of 2P/Encke, which correlate with one of the lowest cometary gas production rates (approx. 2.6 x 10(exp 27) molecules/s) measured thus far in the infrared. This suggests that we are seeing the effects of more efficient radiative cooling, insufficient collisional excitation, and/or inefficient heating by fast H-atoms (and icy grains) in the observed region of the coma. Its extremely short orbital period, very low gas production rate, and classification as an ecliptic comet, make 2PlEncke an important addition to our growing database, and contribute significantly to the establishment of a chemical taxonomy of comets.

Radeva, Yana L.↗

Pre- and Post-perihelion Observations of C/2009 P1 (Garradd): Evidence for an Oxygen-rich Heritage?

We conducted pre- and post-perihelion observations of Comet C/2009 P1 (Garradd) on UT 2011 October 13 and 2012 January 8, at heliocentric distances of 1.83 and 1.57 AU, respectively, using the high-resolution infrared spectrometer (NIRSPEC) at the Keck II 10-m telescope on Mauna Kea, HI. Pre-perihelion, we obtained production rates for nine primary volatiles (native ices): H2O, CO, CH3OH, CH4, C2H6, HCN, C2H2, H2CO, and NH3. Post-perihelion, we obtained production rates for three of these (H2O, CH4, and HCN) and sensitive upper limits for three others (C2H2, H2CO, and NH3). CO was enriched and C2H2 was depleted, yet C2H6 and CH3OH were close to their currentmean values asmeasured in a dominant group of Oort cloud comets. This may indicate processing of its pre-cometary ices in a relatively oxygen-rich environment. Our measurements indicate consistent pre- and post-perihelion abundance ratios relative to H2O, suggesting we were measuring compositional homogeneity among measured species to the depths in the nucleus sampled. However, the overall gas production was lower post-perihelion despite its smaller heliocentric distance on January 8. This is qualitatively consistent with other studies of C/2009 P1, perhaps due to seasonal differences in the heating of one or more active regions on the nucleus. On October 13, the water profile showed a pronounced excess towards the Sun-facing hemisphere that was not seen in other molecules, including H2O on January 8, nor in the dust continuum. Inter-comparison of profiles from October 13 permitted us to quantify contributions due to release of H2O from the nucleus, and fromits release in the coma. This resulted in the latter source contributing 25-30% of the total observed water within our slit, which covered roughly +/-300 km by +/-4500 km from the nucleus. We attribute this excess H2O, which peaked at a mean projected distance of 1300-1500 km from the nucleus, to release from water-rich, relatively pure icy grains

Volatile composition↗

The Composition of Comet C 2012 K1 (PanSTARRS) and the Distribution of Primary Volatile Abundances Among Comets

On 2014 May 22 and 24 we characterized the volatile composition of the dynamically new Oort cloud comet C2012 K1 (PanSTARRS) using the long-slit, high resolution ( lambda/delta lambda is approximately or equal to 25,000) near-infrared echelle spectrograph (NIRSPEC) at the 10 m Keck II telescope on Maunakea, Hawaii. We detected fluorescent emission from six primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, and CO). Upper limits were derived for C2H2, NH3, and H2CO. We report rotational temperatures, production rates, and mixing ratios (relative to water). Compared with median abundance ratios for primary volatiles in other sampled Oort cloud comets, trace gas abundance ratios in C2012 K1 (PanSTARRS) for CO and HCN are consistent, but CH3OH and C2H6 are enriched while H2CO, CH4, and possibly C2H2 are depleted. When placed in context with comets observed in the near- infrared to date, the data suggest a continuous distribution of abundances of some organic volatiles (HCN, C2H6, CH3OH, CH4) among the comet population. The level of enrichment or depletion in a given comet does not necessarily correlate across all molecules sampled, suggesting that chemical diversity among comets may be more complex than the simple organics-enriched, organics-normal, and organics-depleted framework.

Roth, Nathan X.↗

A Tale of "Two" Comets: The Primary Volatile Composition of Comet 2P/Encke Across Apparitions and Implications for Cometary Science

The highly favorable 2017 apparition of 2P/Encke allowed the first comprehensive comparison of primary volatile abundances in a given comet across multiple apparitions. This apparition offered opportunities to address pressing questions in cometary science, including investigating evolutionary and/or heliocentric distance (R(sub h)) effects on volatile production, sampling the hypervolatiles CO and CH4 in an ecliptic comet, and measuring volatile release at small R(sub h). The faintness and frequently low geocentric velocity of ecliptic comets during most apparitions make our near-infrared observations of these hypervolatiles rare and of high scientific impact. We characterized the volatile composition of 2P/Encke on three post-perihelion dates using the iSHELL spectrograph at the NASA Infrared Telescope Facility on Maunakea, HI. We detected fluorescent emission from nine primary volatiles (H2O, CO, C2H6, CH3OH, CH4, H2CO, NH3, OCS, and HCN) and three fragment species (OH*, NH2, and CN), and obtained a sensitive upper limit for C2H2. We report rotational temperatures, production rates, and mixing ratios (abundances relative to H2O). Compared to mean abundances in comets observed to date in the near-infrared, mixing ratios of trace gases in 2P/Encke were depleted for all species except H2CO and NH3, which were “normal.” The detection of the hypervolatiles CO and CH4 is particularly notable given the paucity of measurements in ecliptic comets. We observed significant differences in primary volatile composition compared to published pre-perihelion results from 2003 at larger R(sub h). We discuss possible mechanisms for these differences and discuss these results in the context of findings from the Rosetta mission and ground-based studies of comets.

Roth, Nathan X.↗