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Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). 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) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗

Titan's Stratospheric Condensibles at High Northern Latitudes During Northern Winter

The Infrared Interferometer Spectrometer (IRIS) instrument on board Voyager 1 caught the first glimpse of an unidentified particulate feature in Titan's stratosphere that spectrally peaks at 221 per centimeter. Until recently, this feature that we have termed 'the haystack,' has been seen persistently at high northern latitudes with the Composite Infrared Spectrometer (CIRS) instrument onboard Cassini, The strength of the haystack emission feature diminishes rapidly with season, becoming drastically reduced at high northern latitudes, as Titan transitions from northern winter into spring, In contrast to IRIS whose shortest wavenumber was 200 per centimeter, CIRS extends down to 10 per centimeter, thus revealing an entirely unexplored spectral region in which nitrile ices have numerous broad lattice vibration features, Unlike the haystack, which is only found at high northern latitudes during northern winter/early northern spring, this geometrically thin nitrile cloud pervades Titan's lower stratosphere, spectrally peaking at 160 per centimeter, and is almost global in extent spanning latitudes 85 N to 600 S, The inference of nitrile ices are consistent with the highly restricted altitude ranges over which these features are observed, and appear to be dominated by a mixture of HCN and HC3N, The narrow range in altitude over which the nitrile ices extend is unlike the haystack, whose vertical distribution is significantly broader, spanning roughly 70 kilometers in altitude in Titan's lower stratosphere, The nitrile clouds that CIRS observes are located in a dynamically stable region of Titan's atmosphere, whereas CH4 clouds, which ordinarily form in the troposphere, form in a more dynamically unstable region, where convective cloud systems tend to occur. In the unusual situation where Titan's tropopause cools significantly from the HASI 70.5K temperature minimum, CH4 should condense in Titan's lower stratosphere, just like the aforementioned nitrile clouds, although in significantly larger abundances. We will present the spectral and vertical distribution of Titan's stratospheric particulates during northern winter on Titan. The drastically changing abundance of the haystack over a small latitude range will be highlighted, specifically comparing the IRIS and CIRS epochs, Finally, we will discuss the situation in which CH4 condenses in Titan's lower stratosphere, forming an unexpected quasi steady-state stratospheric Ice cloud.

Anderson, Carrie↗

Regolith Volatile Characterization (RVC) in RESOLVE

Resource investigation in the lunar poles is of importance to the potential impact of in-situ resource utilization (ISRU). The RESOLVE project developed a payload to investigate the permanently shadowed areas of the lunar poles and demonstrate ISRU technology. As a part of the RESOLVE project, the regolith volatile characterization (RVC) subsystem was designed to examine the release of volatiles from sample cores. The test sample was heated in the reactor to release the volatiles where they were analyzed with gas chromatography. Subsequently, the volatile sample was introduced into the lunar water resource demonstration (LWRD) subsystem where the released hydrogen and water were selectively captured. The objective of the Regolith Volatile Characterization (RVC) subsystem was to heat the crushed core sample and determine the desorption of volatile species of interest. The RVC subsystem encompasses the reactor and the system for volatile analysis. The system was designed to analyze H2, He, CO, CO2, N2, 02, CH4, H2S and H2O. The GC chosen for this work is a Siemens MicroSAM process GC with 3 columns and 8 TCD detectors. Neon was chosen as the carrier gas to enhance the analysis of hydrogen and helium.The limit of detection for the gases is approx.1000ppm for H2, CO. CO2 , N2, O2 and H2 S. The limit of detection for CH4 is approx.4000ppm and the water limit of detection is -10000 ppm with a sample analysis time of 2-3 minutes. These values (with the exception of water and H2S) were determined by dilution of a six gas mixture from Scott Gas (5% CO2, CO, O2, N2, 4% CH4 and H2) using mass flow controllers (MFC5). Water was calibrated at low levels using an in house relative humidity (RH) generator. H 2S and high concentrations of H2 were calibrated by diluting a pure stream of gas with MFCs. Higher concentrations of N2 and 02 were calibrated using Air again diluting with MFCs. There were three modification goals for the GC in EBU2 that would allow this process GC to be used in the field demo for RESOLVE. The first modification was to decrease the weight associated with the GC, this included eliminating the explosion proof case (Figure 1) and replacing it with a lightweight case as well as using an on board COPV tank for the neon carrier gas. The next goal was to add a second oven for the molecular sieve column to allow for dual temperature control during GC operation; the separation of hydrogen and helium is optimum at lower temperatures while the water analysis required higher temperatures creating a competing design requirement. The second oven also allows a lower limit of detection for water quantification and avoids the possibility of water condensing in the GC which could ruin the column characteristics. The final goal was to modify the column arrangement to optimize the system for our specific application. Figure 2 shows the internal details of the module optimized optimized for our field application. The modifications and performance of the gas analysis system will be discussed in detail.

Captain, Janine↗

The Atmospheres of Directly Imaged Planets: Where Has All the Methane Gone?

Methane and ammonia both first appear at lower effective temperatures in brown dwarf atmospheres than equilibrium chemistry models would suggest. This has traditionally been understood as a consequence of vertical mixing timescales being shorter than chemical equilibration timescales in brown dwarf photospheres. Indeed the eddy diffusivity, a variable accounting for the vigor of vertical mixing, has become a standard part of the description of brown dwarf atmosphere models, along with Teff and log g. While some models have suggested that methane is less favored at lower gravity, the almost complete absence of methane in the atmospheres of directly imaged planets, such as those orbiting HR 8799, even at effective temperatures where methane is readily apparent in brown dwarf spectra, has been puzzling. To better understand the paucity of methane in low gravity atmospheres we have revisited the problem of methane chemistry and mixing. We employed a 1-D atmospheric chemistry code augmented with an updated and complete network of the chemical reactions that link CO to CH4. We find the methane abundance at altitudes at or above the effective photosphere is a strong function of surface gravity because higher g shifts the p-T structure to higher pressures (i.e., a given optical depth is proportional to p/g, a relation mitigated somewhat by pressure broadening). Thus quenching in more massive brown dwarfs occurs at a lower temperature and higher pressure, both favoring CH4. We predict that in the lowest mass young giant planets, methane will appear very late, at effective temperatures as low as 600 K rather than the 1200 K seen among field brown dwarfs. This methane deficiency has important implications for the interpretation of spectra as well as methane-based planetary companion searches, such as the NICI survey. The GPI and SPHERE surveys will test these ideas and probe atmospheric chemistry and composition in an entire new range of parameter space. A caveat is that these calculations presume that the C to O ratio is comfortably less than one; the behavior is quite different if C and O are equally abundant, and of course CH4 is always present if C exceeds O.

young giant planets↗

The Unexpectedly Bright Comet C-2012 F6 (Lemmon) Unveiled at Near-Infrared Wavelengths

We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R h) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R h = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R h = 0.75 AU with CSHELL (on March 31 and April 1) and R h = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H2O, OH* prompt emission, C2H6, CH3OH, H2CO, HCN, CO, CH4, NH3, and NH2), and obtained upper limits for two others (C2H2 and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 +/- 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3σ) upper limit for HDO corresponds to D/H < 2.45 × 10-3 (i.e., <16 Vienna Standard Mean Ocean Water, VSMOW). At R h = 1.2 AU (CRIRES), the production rate for water was Q(H2O) = 1.9 +/- 0.1 × 1029 s-1 and its rotational temperature was T rot ~ 69 K. At R h = 0.75 AU (CSHELL), we measured Q(H2O) = 4.6 +/- 0.6 × 1029 s-1 and T rot = 80 K on March 31, and 6.6 +/- 0.9 × 1029 s-1 and T rot = 100 K on April 1. At R h = 1.74 AU (NIRSPEC), we obtained Q(H2O) = 1.1 +/- 0.1 × 1029 s-1 and T rot ~ 50 K. The measured volatile abundance ratios classify comet C/2012 F6 as rather depleted in C2H6 and CH3OH, while HCN, CH4, and CO displayed abundances close to their median values found among comets. H2CO was the only volatile showing a relative enhancement. The relative paucity of C2H6 and CH3OH (with respect to H2O) suggests formation within warm regions of the nebula. However, the normal abundance of HCN and hypervolatiles CH4 and CO, and the enhancement of H2CO, may indicate a possible heterogeneous nucleus of comet C/2012 F6 (Lemmon), possibly as a result of radial mixing within the protoplanetary disk

C/2012 F6↗

Pluto and Charon Seen with the New Horizons Spacecraft

After nearly a decade en route, New Horizons flew through the Pluto system in July 2015. The encounter hemisphere of Pluto shows ongoing surface geological activity centered on a vast basin (Sputnik Planum [SP]*) containing a thick layer of volatile ices with a crater retention age no greater than approximately 10 Ma. Surrounding terrains show active glacial flow, apparent transport and rotation of large buoyant water-ice crustal blocks, and pitting, likely by sublimation erosion and/or collapse. Also seen are constructional mounds with central depressions, and ridges with complex bladed textures. Pluto has ancient cratered terrains up to approximately 4 Ga old that are fractured and mantled, and perhaps eroded by glacial processes. Charon does not appear to be currently active, but experienced major tectonism and resurfacing nearly 4 Ga ago. Imaging spectrometer observations of Pluto reveal the encounter hemisphere to be dominated by volatile ices of N2, CO, and CH4, along with non-volatile components that include H2O and tholins. The most volatile of Pluto's ices (N2 and CO) are especially prevalent in the western half of Tombaugh Regio (TR), and the strikingly flat Sputnik Planum basin, which lies a few km below surrounding elevations. The high mobility of N2 and CO ices enables SP's surface to refresh itself sufficiently rapidly that no impact craters are seen there. This likely occurs through a combination of solid state convective overturning and sublimation/ condensation that produces regular patterns of pits and ridges on scales of 102 to 103 m. In many areas, CH4 appears to favor topographically high regions. Its propensity to condense on ridges could play a role in forming the bladed terrain seen in Tartarus Dorsa. H2O can be discerned across much of Cthulhu Regio, and also in a few isolated spots. In many regions, H2O ice is associated with reddish tholin coloration. Pluto's atmosphere was probed with the radio science experiment (REX) and the Alice UV spectrometer, as well as imaging at high phase angles. The surface pressure, due mostly to N2, is approximately 11 microbars. Extensive multiple haze layers are seen in the images. Alice has detected hydrocarbons in addition to CH4 in the atmosphere. Since both are inert, H2O ice and tholin could have similar geological behaviors on Pluto, possibly including aeolian transport or mobilization by volatile ice glaciation. While Pluto's H2O ice is sculpted and at least partially veiled by more volatile ices, Charon's heavily cratered H2O ice is exposed globally. H2O ice spectral bands characteristic of crystalline ice are seen everywhere on the encounter hemisphere. Charon's north polar region is strikingly red, possibly the result of the unique thermal environment of Charon's poles, which become exceptionally cold during the long, dark winters. Extremely cold regions on Charon' could cold trap gases expanding outward from Pluto as ices, and thereby subject them to rapid radiolytic processing. Charon also exhibits a weak NH3 absorption band over most or all of its surface, with small local concentrations. Detailed results of the radio science, small satellite, particles and plasma, and atmosphere investigations are in press.

Pluto↗

The THS Experiment: Simulating Titans Atmospheric Chemistry at Low Temperature (200K)

In Titan's atmosphere, composed mainly of N2 (95-98%) and CH4 (2-5%), a complex chemistry occurs at low temperature, and leads to the production of heavy organic molecules and subsequently solid aerosols. Here, we used the Titan Haze Simulation (THS) experiment, an experimental setup developed at the NASA Ames COSmIC simulation facility to study Titan's atmospheric chemistry at low temperature. In the THS, the chemistry is simulated by plasma in the stream of a supersonic expansion. With this unique design, the gas is cooled to Titan-like temperature ( approximately 150K) before inducing the chemistry by plasma, and remains at low temperature in the plasma discharge (approximately 200K). Different N2-CH4-based gas mixtures can be injected in the plasma, with or without the addition of heavier precursors present as trace elements on Titan, in order to monitor the evolution of the chemical growth. Both the gas- and solid phase products resulting from the plasma-induced chemistry can be monitored and analyzed using a combination of complementary in situ and ex situ diagnostics. A recent mass spectrometry[1] study of the gas phase has demonstrated that the THS is a unique tool to probe the first and intermediate steps of Titan's atmospheric chemistry at Titan-like temperature. In particular, the mass spectra obtained in a N2-CH4-C2H2-C6H6 mixture are relevant for comparison to Cassini's CAPS-IBS instrument. The results of a complementary study of the solid phase are consistent with the chemical growth evolution observed in the gas phase. Grains and aggregates form in the gas phase and can be jet deposited on various substrates for ex situ analysis. Scanning Electron Microscopy images show that more complex mixtures produce larger aggregates. A mass spectrometry analysis of the solid phase has detected the presence of aminoacetonitrile, a precursor of glycine, in the THS aerosols. X-ray Absorption Near Edge Structure (XANES) measurements also show the presence of imine and nitrile functional groups, showing evidence of nitrogen chemistry. These complementary studies show the high potential of THS to better understand Titan's chemistry and the origin of aerosol formation.

Laboratory↗

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.↗

Impact Delivery of Reduced Greenhouse Gases on Early Mars

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form - as proposed by Ramirez et al. [1], later refined by Wordsworth et al. [2], and confirmed by Ramirez [3] - collision induced absorptions between CO2-H2 or CO2-CH4 provide enough extra greenhouse power to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. To raise surface temperatures significantly by this mechanism, surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level. Both Wordsworth et al. [2] and Ramirez [3] show that the melting point can be reached in atmospheres with 1-2 bars of CO2 and 2-10% H2; smaller concentrations of H2 will suffice if CH4 is also present. If thick weakly reducing atmospheres are the solution to the faint young Sun paradox, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks.

greenhose gases↗

Warming Early Mars by Impact Degassing of Reduced Greenhouse Gases

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.

Haberle, R. M.↗

Proposed Trace Gas Measurements Over the Western United States for TROPOMI Validation

The Alpha Jet Atmospheric eXperiment (AJAX), located in the Bay Area of California, is a joint effort between NASA Ames Research Center and H211, LCC. AJAX makes in-situ airborne measurements of trace gases 2-4 times per month, resulting in over 216 flights since 2011. Current measurements include ozone (O3), carbon dioxide (CO2), methane (CH4), water (H2O), formaldehyde (HCHO), and meteorological measurements (i.e., ambient pressure, temperature, and 3D winds). Currently, the AJAX team is working to incorporate nitrogen dioxide (NO2) measurements with a Cavity Attenuated Phase Shift Spectrometer (CAPS). Successful science flights coincident with satellite overpasses have been performed since 2011 by the Alpha Jet, with more than 40 flights under the Greenhouse Observing SATellite (GOSAT) and several flights under the Orbiting Carbon Observatory-2 (OCO-2). Results from these flights, which have covered a range of different surfaces and seasonal conditions, will be presented. In-situ vertical profiles of O3, CO2, CH4, H2O, HCHO, and NO2 from the surface to 28,000 feet made by AJAX will also be valuable for satellite validation of data products obtained from the TROPOspheric Montoring Instrument (TROPOMI). TROPOMI is on board the Copernicus Sentinel-5 precursor (S5p) satellite, with level 2 products including O3, CO, CH4, HCHO, NO2, and aerosols.

Parworth, Caroline L.↗

Extremely Organic-Rich Coma of Comet C/2010 G2 (HILL) During Its Outburst in 2012

We performed high-dispersion near-infrared spectroscopic observations of comet C/2010 G2 (Hill) at 2.5 AU from the Sun using NIRSPEC (R approx. equal to 25,000) at the Keck II Telescope on UT 2012 January 9 and 10, about a week after an outburst had occurred. Over the two nights of our observations, prominent emission lines of CH4 and C2H6, along with weaker emission lines of H2O, HCN, CH3OH, and CO were detected. The gas production rate of CO was comparable to that of H2O during the outburst. The mixing ratios of CO, HCN, CH4, C2H6, and CH3OHwith respect to H2O were higher than those for normal comets by a factor of five or more. The enrichment of COand CH4 in comet Hill suggests that the sublimation of these hypervolatiles sustained the outburst of the comet. Some fraction of water in the inner coma might exist as icy grains that were likely ejected from nucleus by the sublimation of hypervolatiles. Mixing ratios of volatiles in comet Hill are indicative of the interstellar heritage without significant alteration in the solar nebula.

protoplanetary disks↗

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.↗

Fifty Years of Exploring Pluto: from Telescopes to the New Horizons Mission

Pluto was discovered in 1930 at Lowell Observatory in the belated resumption of a wide-field photographic search originally be-gun at Percival Lowell’s direction prior to his death in 1916. Photometry in the 1950s established the rotation period of 6.4 hours and a color redder than the Sun, but the mass, density, size and albedo were unknown. Near-infrared photometry in 1976 indicated the presence of CH4 frost, suggestive of a relatively high surface albedo and a diameter comparable to the Moon. The large satellite Charon was discovered in 1978, followed by an epoch of mutual transits and occultations of Pluto and Charon from 1985 to 1990, as viewed from Earth. These events resulted in reliable sizes and masses of the two bodies, as well as the orbit of Charon. The mutual events also demonstrated that Pluto and Charon are in locked synchronous rotation and revolution, a configuration unique among the planets. The atmosphere of Pluto was discovered in 1988 from a stellar occultation observed from the Kuiper Airborne Observatory and ground stations, with indications of a haze layer (or a temperature inversion) in the lower atmosphere. Sub-sequent stellar occultations showed that the extent of the atmosphere is variable on a timescale of a few years. The spectroscopic detection of N2 and CO ice in 1993 demonstrated that the atmosphere must be primarily composed of N2, with CH4 and CO as minor components; the spectroscopic detection of gaseous CH4 was reported in 1994.

Cruikshank, D. P.↗

Measurement of CH3D on Titan at Submillimeter Wavelengths

We present the first radio/submillimeter detection of monodeuterated methane (CH3D) in Titan's atmosphere, using archival data from of the Atacama Large Millimeter/submillimeter Array (ALMA). The J (sub K) equals 2 (sub 1) minus 1 (sub 1) and J (sub K) equals 2 (sub 0) minus 1 (sub 0) transitions at 465.235 and 465.250 gigahertz (approximately 0.644 millimeters) were measured at significance levels of 4.6 sigma and 5.7 sigma, respectively. These two lines were modeled using the Non-linear optimal Estimator for MultivariatE spectral analySIS (NEMESIS) radiative transfer code to determine the disk-averaged CH3D volume mixing ratio equals 6.157 times 10 (sup minus 6) in Titan's stratosphere (at altitudes greater than 130 kilometers). By comparison with the CH4 vertical abundance profile measured by Cassini-Huygens mass spectrometry, the resulting value for D/H in CH4 is (1.033 plus or minus 0.081) times 10 (sup minus 4). This is consistent with previous ground-based and in situ measurements from the Cassini-Huygens mission, though slightly lower than the average of the previous values. Additional CH3D observations at higher spatial resolution will be required to determine a value truly comparable with the Cassini-Huygens CH4 measurements, by measuring CH3D with ALMA close to Titan's equator. In the post-Cassini era, spatially resolved observations of CH3D with ALMA will enable the latitudinal distribution of methane to be determined, making this an important molecule for further studies.

Thelen, Alexander E.↗

Capturing Complete Spatial Context in Satellite Observations of Greenhouse Gases

Scientific consensus from a 2015 pre-Decadal Survey workshop highlighted the essential need for a wide-swath (mapping) low earth orbit (LEO) instrument delivering carbon dioxide (CO2), methane (CH4), and carbon monoxide (CO) measurements with global coverage. OCO-2 pioneered space-based CO2 remote sensing, but lacks the CH4, CO and mapping capabilities required for an improved understanding of the global carbon cycle. The Carbon Balance Observatory (CARBO) advances key technologies to enable high-performance, cost-effective solutions for a space-based carbon-climate observing system. CARBO is a compact, modular, 15-30° field of view spectrometer that delivers high-precision CO2, CH4, CO and solar induced chlorophyll fluorescence (SIF) data with weekly global coverage from LEO. CARBO employs innovative immersion grating technologies to achieve diffraction-limited performance with OCO-like spatial (2 x 2 sq.km) and spectral (λ/Δλ≈ 20,000) resolution in a package that is >50% smaller, lighter and more cost-effective. CARBO delivers a 25- to 50-fold increase in spatial coverage compared to OCO-2 with no loss of detection sensitivity. Individual CARBO modules weigh < 20 kg, opening diverse new space-based platform opportunities.

Miller, Charles E.↗

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↗