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Comet C/2017 K2 (Pan-STARRS) provided a rare opportunity to investigate the evolution of coma composition and outgassing patterns over a transitional heliocentric distance (Rh) range where activity drivers in comets are thought to change from "hypervolatile" (CO, CH$_4$, C$_2$H$_6$, and/or CO$_2$)-dominated to H2O-dominated. We performed high-resolution, cross-dispersed, near-infrared spectroscopy of C/2017 K2 with iSHELL at the NASA Infrared Telescope Facility (IRTF) and NIRSPEC at the W. M. Keck 2 Observatory. We report gas rotational temperatures (Trot) and molecular production rates (Q; mol/s) or upper limits for the hypervolatile species CH$_4$, CO, and C$_2$H$_6$, together with less volatile ices (CH$_3$OH, H$_2$O, HCN, C$_2$H$_2$, NH$_3$, and OCS) over a range of pre-perihelion distances, Rh= 3.15 - 2.35 au. We also report (or stringently constrain) abundance ratios (mixing ratios) of the targeted species with respect to CO, C$_2$H$_6$, and (when detected) H$_2$O. All volatiles were enriched relative to water in C/2017 K2 when compared to their mean values among Oort Cloud comets, whereas abundances relative to C2H6 were consistent with their average values from other long-period comets., Comment: Submitted to the Astronomical Journal for publication

The SALTUS Probe mission will provide a powerful far-infrared (far-IR) pointed space observatory to explore our cosmic origins and the possibility of life elsewhere. The observatory employs an innovative deployable 14-m aperture, with a sunshield that will radiatively cool the off-axis primary to <45K. This cooled primary reflector works in tandem with cryogenic coherent and incoherent instruments that span the 34 to 660 micron far-IR range at both high and moderate spectral resolutions., Comment: 49 pages, 10 figures, 3 tables, submitted to SPIE JATIS

The extraordinary 2021 September-October outburst of Centaur 29P/Schwassmann-Wachmann 1 afforded an opportunity to test the composition of primitive Kuiper disk material at high sensitivity. We conducted nearly simultaneous multi-wavelength spectroscopic observations of 29P/Schwassmann-Wachmann 1 using iSHELL at the NASA Infrared Telescope Facility and nFLASH at the Atacama Pathfinder EXperiment (APEX) on 2021 October 6, with follow-up APEX/nFLASH observations on 2021 October 7 and 2022 April 3. This coordinated campaign between near-infrared and radio wavelengths enabled us to sample molecular emission from a wealth of coma molecules and to perform measurements that cannot be accomplished with either wavelength alone. We securely detected CO emission on all dates with both facilities, including velocity-resolved spectra of the CO (J=2-1) transition with APEX/nFLASH and multiple CO (v=1-0) rovibrational transitions with IRTF/iSHELL. We report rotational temperatures, coma kinematics, and production rates for CO and stringent (3-sigma) upper limits on abundance ratios relative to CO for CH4, C2H6, CH3OH, H2CO, CS, and OCS. Our upper limits for CS/CO and OCS/CO represent their first values in the literature for this Centaur. Upper limits for CH4, C2H6, CH3OH, and H2CO are the most stringent reported to date, and are most similar to values found in ultra CO-rich Oort cloud comet C/2016 R2 (PanSTARRS), which may have implications for how ices are preserved in cometary nuclei. We demonstrate the superb synergy of coordinated radio and near-infrared measurements, and advocate for future small body studies that jointly leverage the capabilities of each wavelength.

Comets provide a valuable window into the chemical and physical conditions at the time of their formation in the young solar system. We seek insights into where and when these objects formed by comparing the range of abundances observed for nine molecules and their average values across a sample of 29 comets to the predicted midplane ice abundances from models of the protosolar nebula. Our fiducial model, where ices are inherited from the interstellar medium, can account for the observed mixing ratio ranges of each molecule considered, but no single location or time reproduces the abundances of all molecules simultaneously. This suggests that each comet consists of material processed under a range of conditions. In contrast, a model where the initial composition of disk material is `reset', wiping out any previous chemical history, cannot account for the complete range of abundances observed in comets. Using toy models that combine material processed under different thermal conditions we find that a combination of warm (CO-poor) and cold (CO-rich) material is required to account for both the average properties of the Jupiter-family and Oort cloud comets, and the individual comets we consider. This could occur by the transport (either radial or vertical) of ice-coated dust grains in the early solar system. Comparison of the models to the average Jupiter-family and Oort cloud comet compositions suggest the two families formed in overlapping regions of the disk, in agreement with the findings of A'Hearn et al. (2012) and with the predictions of the Nice model (Gomes et al. 2005, Tsiganis et al. 2005)., Comment: 32 pages, 8 figures

We report the detection of CH$_3$OH emission in comet 46P/Wirtanen on UT 2018 December 8 and 9 using the Atacama Compact Array (ACA), part of the Atacama Large Millimeter/Submillimeter Array (ALMA). These interferometric measurements of CH$_3$OH along with continuum emission from dust probed the inner coma ($<$2000 km from the nucleus) of 46P/Wirtanen approximately one week before its closest approach to Earth ($\Delta$ = 0.089 -- 0.092 au), revealing rapidly varying and anisotropic CH$_3$OH outgassing during five separate ACA executions between UT 23:57 December 7 and UT 04:55 December 9, with a clear progression in the spectral line profiles over a timescale of minutes. We present spectrally integrated flux maps, production rates, rotational temperatures, and spectral line profiles of CH$_3$OH during each ACA execution. The variations in CH$_3$OH outgassing are consistent with Wirtanen's 9 hr nucleus rotational period derived from optical and millimeter wavelength measurements and thus are likely coupled to the changing illumination of active sites on the nucleus. The consistent blue offset of the line center indicates enhanced CH$_3$OH sublimation from the sunward hemisphere of the comet, perhaps from icy grains. These results demonstrate the exceptional capabilities of the ACA for time-resolved measurements of comets such as 46P/Wirtanen.

The study of comets affords a unique window into the birth, infancy, and subsequent history of the solar system. There is strong evidence that comets incorporated pristine interstellar material as well as processed nebular matter, providing insights into the composition and prevailing conditions over wide swaths of the solar nebula at the time of planet formation. Dynamically new Oort cloud comets harbor primitive ices that have been stored thousands of astronomical units from the Sun and have suffered minimal thermal or radiative processing since their emplacement ~4.5 Gyr ago. Periodic, more dynamically evolved comets such as the Halley-type and Jupiter-family comets reveal the effects of lives spent over a range of heliocentric distances, including perihelion passages into the very inner solar system. Systematically characterizing the information imprinted in the native ice compositions of these objects is critical to understanding the formation and evolution of the solar system, the presence of organic matter and water on the terrestrial planets, the chemistry present in protoplanetary disks around other stars, and the nature of interstellar interlopers such as 2I/Borisov. Although comet rendezvous and sample return missions can provide remarkable insights into the properties of a few short-period comets, the on-sky capacity necessary to perform population-level comet studies while simultaneously remaining sensitive to the paradigm-challenging science that individual comets can reveal can only be provided by remote sensing observations. Here we report the state-of-the-art in ground- and space-based remote sensing of cometary volatiles, review the remarkable progress of the previous decade, articulate the pressing questions that ground- and space-based work will address over the next ten years, and advocate for the technology and resources necessary to realize these aspirations., Comment: White paper for the National Academies of Sciences, Engineering, and Medicine Planetary Science and Astrobiology Decadal Survey 2023-2032

We present high spectral resolution optical spectra obtained with the ARCES instrument at Apache Point Observatory showing detection of the [OI]6300 A line in interstellar comet 2I/Borisov. We employ the observed flux in this line to derive an H$_2$O production rate of (6.3$\pm$1.5)$\times$10$^{26}$ mol s$^{-1}$. Comparing to previously reported observations of CN, this implies a CN/H$_2$O ratio of $\sim$0.3-0.6%. The lower end of this range is consistent with the average value in comets, while the upper end is higher than the average value for Solar System comets, but still within the range of observed values. C$_2$/H$_2$O is depleted, with a value likely less than 0.1%. The dust-to-gas ratio is consistent with the normal value for Solar System comets. Using a simple sublimation model we estimate an H$_2$O active area of 1.7 km$^2$, which for current estimates for the size of Borisov suggests active fractions between 1-150%, consistent with values measured in Solar System comets. More detailed characterization of 2I/Borisov, including compositional information and properties of the nucleus, is needed to fully interpret the observed H$_2$O production rate., Comment: 8 pages, 2 figures, 1 table, Accepted in ApJ Letters

Comet C/2016 R2 (PanSTARRS) has a peculiar volatile composition, with CO being the dominant volatile as opposed to H$_2$O and one of the largest N$_2$/CO ratios ever observed in a comet. Using observations obtained with the \textit{Spitzer Space Telescope}, NASA's Infrared Telescope Facility, the 3.5-meter ARC 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. We confirm the high abundances of CO and N$_2$ and heavy depletions of H$_2$O, HCN, CH$_3$OH, and H$_2$CO compared to CO reported by previous studies. We provide the first measurements (or most sensitive measurements/constraints) on H$_2$O, CO$_2$, CH$_4$, C$_2$H$_6$, OCS, C$_2$H$_2$, and NH$_3$, all of which are depleted relative to CO by at least one to two orders of magnitude compared to values commonly observed in comets. The observed species also show strong enhancements relative to H$_2$O, and even when compared to other species like CH$_4$ or CH$_3$OH most species show deviations from typical comets by at least a factor of two to three. The only mixing ratios found to be close to typical are CH$_3$OH/CO$_2$ and CH$_3$OH/CH$_4$. While R2 PanSTARRS was located at a heliocentric distance of 2.8 AU at the time of our observations in January/February 2018, we argue 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., Comment: 36 pages, 12 figures, 7 tables, accepted for publication in AJ

We present H$_2$O production rates for comet C/2012 S1 (ISON) derived from observations of [OI] and OH emission during its inbound leg, covering a heliocentric distance range of 1.8-0.44 AU. Our production rates are in agreement with previous measurements using a variety of instruments and techniques and with data from the various observatories greatly differing in their projected fields of view. The consistent results across all data suggest the absence of an extended source of H$_2$O production, for example sublimation of icy grains in the coma, or a source with spatial extent confined to the dimensions of the smallest projected field of view (in this case $<$ 1,000 km). We find that ISON had an active area of around 10 km$^2$ for heliocentric distances R$_h$ > 1.2 AU, which then decreased to about half this value from R$_h$=1.2-0.9 AU. This was followed by a rapid increase in active area at about R$_h$=0.6 AU, corresponding to the first of three major outbursts ISON experienced inside of 1 AU. The combination of a detected outburst in the light curve and rapid increase in active area likely indicates a major nucleus fragmentation event. The 5-10 km$^2$ active area observed outside of R$_h$=0.6 AU is consistent with a 50-100% active fraction for the nucleus, larger than typically observed for cometary nuclei. Although the absolute value of the active area is somewhat dependent on the thermal model employed, the changes in active area observed are consistent among models. The conclusion of a 50-100+% active fraction is robust for realistic thermal models of the nucleus. However the possibility of a contribution of a spatially unresolved distribution of icy grains cannot be discounted., Comment: 26 pages, 5 figures, 5 tables, accepted for publication in Icarus

We present analysis of observations of CO2 and OI emission in three comets to measure the CO2 abundance and evaluate the possibility of employing observations of OI emission in comets as a proxy for CO2. We obtained NIR imaging sensitive to CO2 of comets C/2012 K1 (PanSTARRS), C/2012 K5 (LINEAR), and 290P/Jager with the IRAC instrument on Spitzer. We acquired observations of OI emission in these comets with the ARCES echelle spectrometer mounted on the 3.5-meter telescope at Apache Point Observatory and observations of OH with the Swift observatory (PanSTARRS) and with Keck HIRES (Jager). The CO2/H2O ratios derived from the Spitzer images are 12.6 +/- 1.3% (PanSTARRS), 28.9 +/- 3.6% (LINEAR), and 31.3 +/- 4.2% (Jager). These abundances are derived under the assumption that contamination from CO emission is negligible. The CO2 abundance for PanSTARRS is close to the average abundance measured in comets at similar heliocentric distance to date, while the abundances measured for LINEAR and Jager are significantly larger than the average abundance. From the coma morphology observed in PanSTARRS and the assumed gas expansion velocity, we derive a rotation period for the nucleus of about 9.2 hours. Comparison of H2O production rates derived from ARCES and Swift data, as well as other observations, suggest the possibility of sublimation from icy grains in the inner coma. We evaluate the possibility that the OI emission can be employed as a proxy for CO2 by comparing CO2/H2O ratios inferred from the OI lines to those measured directly by Spitzer. We find that for PanSTARRS we can reproduce the observed CO2 abundance to an accuracy of ~20%. For LINEAR and Jager, we were only able to obtain upper limits on the CO2 abundance inferred from the OI lines. These upper limits are consistent with the CO2 abundances measured by Spitzer., Comment: 30 pages, 6 tables, 7 figures, accepted for publication in Icarus

We present analysis of high spectral resolution NIR spectra of CO and H$_2$O in comet C/2009 P1 (Garradd) taken during its 2011-2012 apparition with the CSHELL instrument on NASA's Infrared Telescope Facility (IRTF). We also present analysis of observations of atomic oxygen in comet Garradd obtained with the ARCES echelle spectrometer mounted on the ARC 3.5-meter telescope at Apache Point Observatory and the Tull Coude spectrograph on the Harlan J. Smith 2.7-meter telescope at McDonald Observatory. The observations of atomic oxygen serve as a proxy for H$_2$O and CO$_2$. We confirm the high CO abundance in comet Garradd and the asymmetry in the CO/H$_2$O ratio with respect to perihelion reported by previous studies. From the oxygen observations, we infer that the CO$_2$/H$_2$O ratio decreased as the comet moved towards the Sun, which is expected based on current sublimation models. We also infer that the CO$_2$/H$_2$O ratio was higher pre-perihelion than post-perihelion. We observe evidence for the icy grain source of H$_2$O reported by several studies pre-perihelion, and argue that this source is significantly less abundant post-perihelion. Since H$_2$O, CO$_2$, and CO are the primary ices in comets, they drive the activity. We use our measurements of these important volatiles in an attempt to explain the evolution of Garradd's activity over the apparition., Comment: 35 pages, 10 figures, 9 tables, accepted for publication in Icarus

Volatile organic emissions were detected post-perihelion in the long period comet C/2006 M4 (SWAN) in October and November 2006. Our study combines target-of-opportunity observations using the infrared Cryogenic Echelle Spectrometer (CSHELL) at the NASA-IRTF 3-m telescope, and millimeter wavelength observations using the Arizona Radio Observatory (ARO) 12-m telescope. Five parent volatiles were measured with CSHELL (H2O, CO, CH3OH, CH4, and C2H6), and two additional species (HCN and CS) were measured with the ARO 12-m. These revealed highly depleted CO and somewhat enriched CH3OH compared with abundances observed in the dominant group of long-period (Oort cloud) comets in our sample and similar to those observed recently in Comet 8P/Tuttle. This may indicate highly efficient H-atom addition to CO at very low temperature (~ 10 - 20 K) on the surfaces of interstellar (pre-cometary) grains. Comet C/2006 M4 had nearly "normal" C2H6 and CH4, suggesting a processing history similar to that experienced by the dominant group. When compared with estimated water production at the time of the millimeter observations, HCN was slightly depleted compared with the normal abundance in comets based on IR observations but was consistent with the majority of values from the millimeter. The ratio CS/HCN in C/2006 M4 was within the range measured in ten comets at millimeter wavelengths. The higher apparent H-atom conversion efficiency compared with most comets may indicate that the icy grains incorporated into C/2006 M4 were exposed to higher H-atom densities, or alternatively to similar densities but for a longer period of time., Comment: Accepted for Publication in Icarus (27 pages, 4 tables, 4 figures)

High-dispersion (l/dl ~ 25,000) infrared spectra of Comet C/2004 Q2 (Machholz) were acquired on Nov. 28-29, 2004, and Jan. 19, 2005 (UT dates) with NIRSPEC at the Keck-2 telescope on Mauna Kea. We detected H2O, CH4, C2H2, C2H6, CO, H2CO, CH3OH, HCN, and NH3 and we conducted a sensitive search for CH3D. We report rotational temperatures, production rates, and mixing ratios (with respect to H2O) at heliocentric distances of 1.49 AU (Nov. 2004) and 1.21 AU (Jan. 2005). We highlight three principal results: (1) The mixing ratios of parent volatiles measured at 1.49 AU and 1.21 AU agree within confidence limits, consistent with homogeneous composition in the mean volatile release from the nucleus of C/2004 Q2. Notably, the relative abundance of C2H6/C2H2 is substantially higher than those measured in other comets, while the mixing ratios C2H6/H2O, CH3OH/H2O, and HCN/H2O are similar to those observed in comets, referred to as "organics-normal". (2) The spin temperature of CH4 is > 35-38 K, an estimate consistent with the more robust spin temperature found for H2O. (3) We obtained a 3s upper limit of CH3D/CH4 < 0.020 (D/H < 0.005). This limit suggests that methane released from the nucleus of C/2004 Q2 is not dominated by a component formed in extremely cold (near 10 K) environments. Formation pathways of both interstellar and nebular origin consistent with the measured D/H in methane are discussed. Evaluating the relative contributions of these pathways requires further modeling of chemistry including both gas-phase and gas-grain processes in the natal interstellar cloud and in the protoplanetary disk., Comment: Accepted by The Astrophysical Journal

Understanding the cosmogonic record encoded in the parent volatiles stored in cometary nuclei requires investigating whether evolution (thermal or otherwise) has modified the composition of short-period comets during successive perihelion passages. As the most volatile molecules systematically observed in comets, the abundances of CO, CH4, and C2H6 in short-period comets may serve to elucidate the interplay between natal conditions and post-formative evolution in setting present-day composition, yet secure measurements of CO and CH4 in Jupiter-family comets (JFCs) are especially sparse. The highly favorable 2018 apparition of JFC 21P/Giacobini–Zinner enabled a sensitive search for these "hypervolatiles" in a prototypical carbon-chain depleted comet. We observed 21P/Giacobini–Zinner with the iSHELL spectrograph at the NASA Infrared Telescope Facility on four pre-perihelion dates, two dates near-perihelion, and one post-perihelion date. We obtained detections of CO, CH4, and C2H6 simultaneously with H2O on multiple dates. We present rotational temperatures, production rates, and mixing ratios. Combined with previous work, our results may indicate that the hypervolatile coma composition of 21P/Giacobini–Zinner was variable across apparitions as well as within a particular perihelion passage, yet the spread in these measurements is a relatively small fraction of the variation in each molecule from comet to comet. We discuss the implications of our measured hypervolatile content of 21P/Giacobini–Zinner for the evolution of JFCs, and place our results in the context of findings from the Rosetta mission and ground-based studies of comets.

We obtained high-resolution (lambda divided by delta times lambda equals approximately 25,000) pre-perihelion spectra of Comet C/2013 V5 (Oukaimeden) using NIRSPEC at Keck II on UT 2014 September 5-6, and CSHELL (Cryogenic Echelle Spectrograph) at the NASA-Infrared Telescope Facility on September 11-13, altogether spanning a range in heliocentric distance R (sub h) equals 0.789-0.698 astronomical units. We report water production rates, and production rates and abundance ratios relative to co-measured H2O for eight trace molecules: CO, H2CO, CH3OH, CH4, C2H2, C2H6, HCN, and NH3. Our measured water production rates from NIRSPEC ( Near Infra-Red Spectrograph) and CSHELL observations remained relatively constant and were close to those from SOHO (Solar and Heliospheric Observatory) / Solar Wind Anisotropies observations that encompassed our dates, suggesting H2O production dominated by release directly from or within approximately 2000 kilometers of the nucleus. All trace volatiles were depleted relative to their respective median abundances among comets, excepting NH3, which was consistent with its median abundance. Most surprising were pronounced increases in abundance ratios for CH3OH (by 51 percent relative to simultaneously measured H2O) and especially C2H6 (by 87 percent) between September 5 and 6. On September 5, C2H6 was severely depleted, consistent with its lowest abundance yet measured for any comet. It also tracked the spatial profile of H2O, suggesting C2H6 was associated with a polar ice phase dominating gas production. On September 6, C2H6 was only moderately depleted and was spatially distinct from H2O, suggesting both polar- and nonpolar-dominated ice phases contributed to the activity then. Our results are consistent with a nonhomogeneous volatile composition for C/2013V5, implying differential processing of its constituent ices.

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.

We used the new high spectral resolution cross-dispersed facility spectrograph, iSHELL, at the NASA Infrared Telescope Facility on Maunakea, HI, to observe Jupiter-family comet (JFC) 45P/Honda-Mrkos-Pajdusakova. We report water production rates, as well as production rates and abundance ratios relative to H2O, for eight trace parent molecules (native ices), CO, CH4, H2CO, CH3OH, HCN, NH3, C2H2, and C2H6, on 2 days spanning UT 2017 January 6/7 and 7/8, shortly following perihelion. Trace species were measured simultaneously with H2O and/or OH prompt emission, a proxy for H2O production, thereby providing a robust and consistent means of establishing the native ice composition of 45P. Its favorable geocentric radial velocity (approximately minus 35 kilometers per second) permitted sensitive measures of the "hypervolatiles" CO and CH4, which are substantially undercharacterized in JFCs. Our results represent the most precise ground-based measures of CO and CH4 to date in a JFC, providing a foundation for building meaningful statistics regarding their abundances. The abundance ratio for CH4 in 45P (0.79 percent plus or minus 0.06 percent relative to H2O) was consistent with its median value as measured among Oort Cloud comets, whereas CO (0.60 percent plus or minus 0.04 percent) was strongly depleted. Compared with all measured comets, HCN (0.049 percent plus or minus 0.012 percent) was strongly depleted, CH3OH (3.6 percent plus or minus 0.3 percent) was enriched, and the remaining species were consistent with their respective median abundances. The volatile composition measured for 45P could indicate processing of ices prior to their incorporation into its nucleus. Spatial analysis of emissions suggests enhanced release of more volatile species into the sunward-facing hemisphere of the coma.

Comet C/2006 W3 (Christensen) remained outside a heliocentric distance (Rh) of 3.1 au throughout its apparition, but it presented an exceptional opportunity to directly sense a suite of molecules released from its nucleus. The Cryogenic Infrared Echelle Spectrograph at ESO-VLT detected infrared emissions from the three hypervolatiles (CO, CH4, and C2H6) that have the lowest sublimation temperatures among species that are commonly studied in comets by remote sensing. Even at Rh 3.25 au, the production rate of each molecule exceeded those measured for the same species in a number of other comets, although these comets were observed much closer to the Sun. Detections of CO at Rh = 3.25, 4.03, and 4.73 au constrained its post-perihelion decrease in production rate, which most likely dominated the outgassing. At 3.25 au, our measured abundances scaled as CO/CH4/C2H6 approx. = 100/4.4/2.1. The C2H6/CH4 ratio falls within the range of previously studied comets at Rh < 2 au, while CO/CH4 is comparatively high and similar to in situ measurements from Rosetta at approx.10 km from the nucleus of 67P/Churyumov-Gerasimenko conducted at a very similar Rh (3.15 au). The independent detections of H2O (Herschel Space Observatory) and CO (this work) imply a coma abundance H2O/CO approx. = 20% in C/2006 W3 near Rh = 5 au. All these measurements are of high value for constraining models of nucleus sublimation (plausibly CO-driven) beyond Rh = 3au, where molecular detections in comets are still especially sparse.

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.

We performed a sensitive search for HDO in comet D/2012 S1 (ISON) on 2013 November 16, 17, and 22 using CSHELL and the NASA Infrared Telescope Facility. We constrained the HDO/H2O ratio to less than 2.0 VSMOW (the terrestrial ocean value) at the 3 sigma uncertainty level from two independent measurements corresponding to different H2O outgassing rates. This represents the best constrained HDO/H2O ratio for a comet using a small (3 m) telescope and illustrates that when CSHELL is replaced with iSHELL, 3 m class telescopes are still strong contenders for detecting minor volatile species in moderately bright comets.

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.