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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.↗

The Peculiar Volatile Composition of CO-Dominated Comet C/2016 R2 (PanSTARRS)

Comet C/2016 R2 (PanSTARRS) has a peculiar volatile composition, with CO being the dominant volatile, as opposed to H2O, and one of the largest N2/CO ratios ever observed in a comet. Using observations obtained with the Spitzer Space Telescope, NASA’s Infrared Telescope Facility, the 3.5 m Astrophysical Research Consortium telescope at Apache Point Observatory, the Discovery Channel Telescope at Lowell Observatory, and the Arizona Radio Observatory 10 m Submillimeter Telescope, we quantified the abundances of 12 different species in the coma of R2 PanSTARRS: CO, CO2, H2O, CH4, C2H6, HCN, CH3OH, H2CO, OCS, C2H2, NH3, and N2. We confirm the high abundances of CO and N2 and heavy depletions of H2O, HCN, CH3OH, and H2CO compared to CO reported by previous studies. We provide the first measurements (or most sensitive measurements/constraints) on H2O, CO2, CH4, C2H6, OCS, C2H2, and NH3, all of which are depleted relative to CO by at least 1–2 orders of magnitude compared to values commonly observed in comets. The observed species also show strong enhancements relative to H2O, and, even when compared to other species like CH4 or CH3OH, most species show deviations from typical comets by at least a factor of 2–3. The only mixing ratios found to be close to typical are CH3OH/CO2 and CH3OH/CH4. The CO2/CO ratio is within a factor of 2 of those observed for C/1995 O1 (Hale- Bopp) and C/2006 W3 (Christensen) at a similar heliocentric distance, though it is at least an order of magnitude lower than many other comets observed with AKARI. While R2 PanSTARRS was located at a heliocentric distance of 2.8 au at the time of our observations in 2018 January/February, we argue, using sublimation models and comparison to other comets observed at similar heliocentric distance, that this alone cannot account for the peculiar observed composition of this comet and therefore must reflect its intrinsic composition. We discuss possible implications for this clear outlier in compositional studies of comets obtained to date and encourage future dynamical and chemical modeling in order to better understand what the composition of R2 PanSTARRS tells us about the early solar system.

McKay, Adam J.↗

Post-Perihelion Volatile Production and Release from Jupiter-Family Comet 45P/Honda-Mrkos-Pajdušáková

High-resolution infrared spectra of Jupiter-family comet 45P/Honda-Mrkos-Pajdušáková were obtained with NIRSPEC at the W. M. Keck Observatory on two post- perihelion dates (UT 2017 February 13 and 19), when the comet was at heliocentric distances of 1.01 and 1.10 AU, respectively. On UT February 13, H2O was measured simultaneously with six trace parent molecules: CH3OH, C2H6, HCN, NH3, C2H2, and H2CO. On UT February 19, CH4 and CO were also targeted in addition to the species measured on UT February 13. Abundances of CO, CH4, and C2H2 relative to H2O are consistent with values obtained from IRTF/iSHELL observations of 45P in early January 2017 just after perihelion when the heliocentric distance was 0.55–0.56 AU. Differences are seen in H2CO/H2O, C2H6/H2O, CH3OH/H2O, and HCN/H2O in February compared to January. Additionally, NH3 abundances appear highly variable during the February measurements, suggesting possible fluctuations of a factor of ten; however, there is significant uncertainty in quantifying NH3 owing to the marginal detections of only one or two lines on each of the two dates. Combining all infrared spectroscopic observations of 45P in January and February 2017, a post-perihelion relationship of Q(H2O) = (2.81 ± 0.25) × 10(exp 27) [R(sub h) (sup −3.83 ± 0.18)] molecules/s is derived. However, all measurements suggest significant variability in H O production on timescales of hours and days. Compared to other comets, volatile abundances relative to H2O in 45P are as follows: CO (depleted relative to all measured comets), CH3OH (enriched/all comets), CH4 and C2H6 (typical/all comets, enriched/Jupiter-family comets), C2H2 (depleted/all comets, typical/Jupiter-family comets), H2CO (January: typical, February depleted/all comets), HCN (January: severely depleted, February: typical/Jupiter-family comets). The small geocentric distances of the comet in February 2017 provide high spatial resolution in the coma of 45P (~12 and 19 km/pixel on February 13 and 19, respectively). Overall, the spatial distributions of volatiles and dust suggest a relatively symmetric and uniform coma during the UT February 13 and 19 observations, with small spatial differences noted between some volatile species. Measured C2H2 and HCN abundances are consistent with HCN as the primary parent of CN and C2H2 as a significant but not primary parent for C2, based on C2 and CN 2017 and previous apparitions. Extracted spectra show an increase in the dust-to-gas ratio in 45P from February 13 to 19 in agreement with contemporaneous narrowband optical measurements.

Russo, Neil Dello↗

On the origin & thermal stability of Arrokoth's and Pluto's ice

In this paper we discuss in a thermodynamic, geologically empirical way the long-term nature of the stable majority ices that could be present in Kuiper Belt object (KBO) 2014 MU69 (also called Arrokoth; hereafter “MU(69)”) after its 4.6 Gyr residence in the Edgeworth-Kuiper belt (EKB) as a cold classical object. We compare the upper bounds for the gas production rate (~10^(24) molecules/s) measured by the New Horizons (NH) spacecraft flyby on 01 Jan 2019 to estimates for the outgassing flux rates from a suite of common cometary and KBO ices at the average ~ 40 K sunlit surface temperature of MU69, but do not find the upper limit very constraining except for the most volatile of species (e.g. CO, N2, CH4). More constraining is the stability versus sublimation into vacuum requirement over Myr to Gyr, and from this we find only 3 common ices that are truly refractory: HCN, CH3OH, and H2O (in order of increasing stability), while NH3 and H2CO ices are marginally stable and may be removed by any positive temperature excursions in the EKB, as produced every 10^(8)–10^(9) years by nearby supernovae and passing O/B stars. To date the NH team has reported the presence of abundant CH3OH and H2O on MU69's surface (Stern et al., 2019; Grundy et al., 2020). NH3 has been searched for, but not found. We predict that future absorption feature detections, if any are ever derived from higher signal-to-noise ratio spectra, will be due to an HCN or poly-H2CO based species. Consideration of the conditions present in the EKB region during the formation era of MU69 lead us to state that it is highly likely that it “formed in the dark”, in an optically thick mid-plane, unable to see the nascent, variable, highly luminous Young Stellar Object (YSO)/TTauri Sun, and that KBOs contain HCN and CH3OH ice phases in addition to the H2O ice phases found in their short period (SP) comet descendants. Finally, when we apply our ice thermal stability analysis to bodies/populations related to MU69, we find that methanol ice is likely ubiquitous in the outer solar system; that if Pluto isn't a fully differentiated body, then it must have gained its hypervolatile ices from proto-planetary disk (PPD) sources in the first few Myr of the solar system's existence; and that hypervolatile rich, highly primordial comet C/2016 R2 was placed onto an Oort Cloud orbit on a similar few Myr timescale.

Pluto↗

Volatile Abundances, Extended Coma Sources, and Nucleus Ice Associations in Comet C/2014 Q2 (Lovejoy)

High-resolution infrared spectra of comet C/2014 Q2 Lovejoy were acquired with NIRSPEC at the W. M. Keck Observatory on two post-perihelion dates(UT 2015 February 2 and 3).H2O was measured simultaneously with CO,CH3OH, H2CO, CH4, C2H6,C2H4, C2H2, HCN, and NH3 on both dates, and rotational temperatures, production rates, relative abundances, H2O ortho-to-para ratios, and spatial distributions in the coma were determined. The first detection of C2H4in a comet from ground-based observations is reported. Abundances relative to H2O for all species were found to be in the typical range compared with values for other comets in the overall population to date. There is evidence of variability in rotational temperatures and production rates on timescales that are small compared with the rotational period of the comet. Spatial distributions of volatiles in the coma suggest complex outgassing behavior.CH3OH, HCN, C2H6, and CH4 spatial distributions in the coma are consistent with direct release from associated ices in the nucleus and are peaked in a more sunward direction compared with co-measured dust. H2O spatial profiles are clearly distinct from these other four species, likely due to a sizable coma contribution from icy grain sublimation.Spatial distributions for C2H2,H2CO, and NH3suggest substantial contributions from extended coma sources, providing further evidence for distinct origins and associations for these species in comets. CO shows a different spatial distribution compared with other volatiles, consistent with jet activity from discrete nucleus ice sources.

Neil Dello Russo↗

Research investigation directed toward extending the useful range of the electromagnetic spectrum

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

Hartmann, S. R.↗