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This paper presents results from our molecular characterization of comet 21P/Giacobini-Zinner during its 2018 apparition. We followed the comet during four observing runs, for a total of 8 nights. The high-resolution spectra of 21P were acquired using iSHELL - the near-IR high resolution immersion echelle spectrograph on NASA/IRTF (Mauna Kea, Hawaii). We detected many cometary emission lines across four customized iSHELL settings in the (2.9 – 5.2) μm range. CO abundances relative to water displayed a relatively constant behavior during the observing campaign, suggesting a possible correlation between the outgassing of water and CO. While CO mixing ratios in 21P are consistent with the reference median value for Jupiter Family comets (JFCs), ethane was depleted relative to the reference median value for JFCs, excepting one observing run (8th and 9th Aug) in which ethane appeared overabundant. We consider several possible causes: an ethane outburst, decreasing outgassing of water, or a seasonal effect owing to nucleus rotation. In the pre-perihelion runs, methanol was overabundant compared with the reference median value for JFCs, however it decreased steadily to a depleted value during 21P’s post-perihelion phase, suggesting a possible seasonal effect. We report 3-s upper limits for acetylene, formaldehyde, ammonia and methane. The ratios of our measured 3-s upper limits for acetylene and detections of hydrogen cyanide are consistent with the depletion of C2 relative to CN in 21P observed at optical wavelengths. This result confirms that 21P is depleted in the carbon chain primary volatile responsible for C2 production.

Previous investigations proved the existence of local density enhancements in Europa’s atmosphere, advancing the idea of a possible origination from water plumes. These measurement strategies, however, were sensitive either to total absorption or atomic emissions, which limited the ability to assess the water content. Here we present direct searches for water vapour on Europa spanning dates from February 2016 to May 2017 with the Keck Observatory. Our global survey at infrared wavelengths resulted in non-detections on 16 out of 17 dates, with upper limits below the water abundances inferred from previous estimates. On one date (26 April 2016) we measured 2,095 ± 658 tonnes of water vapour at Europa’s leading hemisphere. We suggest that the outgassing ls than previously estimated, with only rare localized events of stronger activity.

We observed short-period comet 252P/LINEAR post-perihelion during its 2016 passage, which presented a favorable opportunity to survey its chemical composition at a close Earth approach (∼0.14 au). We characterized the comet’s chemical composition on four dates (UT 2016 April 12, 19, 26, and 29) using spectroscopic measurements with the Near-infrared Spectrograph (NIRSPEC) at the Keck Observatory on Maunakea, HI. Our high-resolution infrared spectra yielded production rates for four species (H2O, CH3OH, C2H6, and HCN) and upper limits for five species (NH3, H2CO, C2H2, CO, and CH4). We measured water at an average production rate of 4.9 ± 0.1 × 10(exp 27) molec s(exp -1). The chemical properties of 252P suggest a rather typical composition, yet somewhat enriched in methanol and ethane but low in formaldehyde (upper limit) compared to other short-period comets surveyed at infrared wavelengths. Analysis of the ortho/para ratio in water indicates a nuclear spin temperature larger than ∼38 K, consistent with statistical equilibrium (2σ). Spatial distributions of gases, which are representative of possible heterogeneity in the nucleus and/or gas dynamics upon sublimation, showed rather symmetric profiles, with subtle enhancements of the more volatile species C2H6 and HCN toward the sunward hemisphere, while water showed spatial distributions that were extended toward the anti-sunward hemisphere. The continuum was characterized by a narrow distribution. We place our infrared results in the context of observations with the Discovery Channel Telescope, the James Clerk Maxwell submillimeter Telescope, and the Hubble Space Telescope.

In 2017 April, we acquired comprehensive high-resolution spectra of newly discovered comet C/2017 E4 (Lovejoy) as it approached perihelion, and before its disintegration. We detected many cometary emission lines in the range (2.8-5.3) μm, in four customized instrument settings (L1-c, L3, Lp1-c, and M1) of iSHELL-the new near-IR high-resolution immersion echelle spectrograph at NASA/IRTF (Maunakea, Hawaii). We identified 12 molecular species: nine primary volatiles (H2O, HCN, NH3, CO, C2H2, C2H6, CH4, CH3OH, H2CO) and three product species (CN, NH2, OH). We detected 85 H2O emission lines from 12 water vibrational bands across L1-c and M1 settings. The many detected water emission lines enabled retrieval of accurate measures for ortho- and para-H2O independently, thereby reducing systematic uncertainty in the derived ortho-para ratio and nuclear spin temperature. Excitation analyses and emission profile analyses were performed for all species, and molecular abundance ratios relative to water are compared with values found for other Oort Cloud comets in our infrared database. Abundance ratios are consistent for most species, with the exception of underabundant methanol and overabundant ammonia in E4.

Observations of the sungrazing comet C/2012 S1 (ISON) were carried out using the Atacama Large Millimeter/submillimeter Array at a heliocentric distance of 0.58-0.54 AU (Astronomical Units) (pre-perihelion) on 2013 November 16-17. Temporally resolved measurements of the coma distributions of HNC, CH3OH, H2CO, and dust were obtained over the course of about an hour on each day. During the period UT 10:10-11:00 on November 16, the comet displayed a remarkable drop in activity, manifested as a greater than 42 percent decline in the molecular line and continuum fluxes. The H2CO observations are consistent with an abrupt, approximately 50 percent reduction in the cometary gas production rate soon after the start of our observations. On November 17, the total observed fluxes remained relatively constant during a similar period, but strong variations in the morphology of the HNC distribution were detected as a function of time, indicative of a clumpy, intermittent outflow for this species. Our observations suggest that at least part of the detected HNC originated from degradation of nitrogen-rich organic refractory material, released intermittently from confined regions of the nucleus. By contrast, the distributions of CH3OH and H2CO during the November 17 observations were relatively uniform, consistent with isotropic outflow and stable activity levels for these species. These results highlight a large degree of variability in the production of gas and dust from comet ISON during its pre-perihelion outburst, consistent with repeated disruption of the nucleus interspersed with periods of relative quiescence.

We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H2O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H2O and HDO, yielding production rates of 5.9 +/- 0.13 × 10(exp 29) and 3.6 +/- 1.0 × 10(exp 26) molecules/sec, respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water of 3.02 +/- 0.87 × 10(exp −4), i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 +/- 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 +/- 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H2O.

We present a new quantitative model for detailed solar-pumped fluorescent emission of the main isotopologue of CN. The derived fluorescence efficiencies permit estimation and interpretation of ro-vibrational infrared line intensities of CN in exospheres exposed to solar (or stellar) radiation. Our g-factors are applicable to astronomical observations of CN extending from infrared to optical wavelengths, and we compare them with previous calculations in the literature. The new model enables extraction of rotational temperature, column abundance, and production rate from astronomical observations of CN in the inner coma of comets. Our model accounts for excitation and de-excitation of rotational levels in the ground vibrational state by collisions, solar excitation to the A(sup 2)Pi(sub I) and B(sup 2)Sum(sup +) electronically excited states followed by cascade to ro-vibrational levels of X(sup 2)Sum(sup +), and direct solar infrared pumping of ro-vibrational levels in the X(sup 2)Sum(sup +) state. The model uses advanced solar spectra acquired at high spectral resolution at the relevant infrared and optical wavelengths and considers the heliocentric radial velocity of the comet (the Swings effect) when assessing the exciting solar flux for a given transition. We present model predictions for the variation of fluorescence rates with rotational temperature and heliocentric radial velocity. Furthermore, we test our fluorescence model by comparing predicted and measured line-by-line intensities for X(sup 2)Sum(sup +) (1-0) in comet C/2014 Q2 (Lovejoy), thereby identifying multiple emission lines observed at IR wavelengths.

We report production rates for H2O and eight trace molecules (CO, C2H6, CH4, CH3OH, NH3, H2CO, HCN, C2H2) in the dynamically new, Sun-grazing Comet C2012 S1 (ISON), using high-resolution spectroscopy at Keck II and the NASA IRTF on 10pre-perihelion dates encompassing heliocentric distances Rh1.210.34 AU. Measured water production rates spanned two orders of magnitude, consistent with a long-term heliocentric power law Q(H2O) Rh-3.10.1). Abundance ratios for CO, C2H6, and CH4 with respect to H2O remained constant with Rh and below their corresponding mean values measured among a dominant sample of Oort Cloud comets. CH3OH was also depleted for Rh 0.5 AU, but was closer to its mean value for Rh0.5 AU. The remaining four molecules exhibited higher abundance ratios within 0.5 AU: for Rh 0.8 AU, NH3 and C2H2 were consistent with their mean values while H2CO and HCN were depleted. For Rh 0.5 AU, all four were enriched, with NH3, H2CO, and HCN increasing most. Spatial profiles of gas emission in ISON consistently peaked sunward of the dust continuum, which was asymmetric antisunward and remained singly peaked for all observations. NH3 within 0.5 AU showed a broad spatial distribution, possibly indicating its release in the coma provided that optical depth effects were unimportant. The column abundance ratio NH2H2O at 0.83 AU was close to the typical NHOH from optical wavelengths, but was higher within 0.5 AU. Establishing its production rate and testing its parentage (e.g., NH3) require modeling of coma outflow.

We quantified primary volatiles in comet C/2009 Pl (Garradd) through pre- and post-perihelion observations acquired during its apparition in 2011-12 [1,2,3]. Detected volatiles include H2O, CO, CH4, C2H2, C2H6, HCN, NH3, H2CO, and CH3OH. We present production rates and chemical abundance ratios (relative to water) for all species, and I-D spatial profiles for multiple primary volatiles. We discuss these findings in the context of an emerging taxonomy based on primary volatiles in comets [4]. We used three spectrometer/telescope combinations. On UT 20ll August 7 (Rh 2.4 AU) and September 17-21 (Rh 2.0 AU), we used CRIRES at ESO's Very Large Telescope (VLT) [1]. On September 8 and 9 (Rh 2.1 AU), we used NIRSPEC at Keck-2 and CSHELL at IRTF [2]. Using NIRSPEC on October 13 and 2012 January 08 (Rh 1.83 and 1.57 AU, respectively), we detected nine primary volatiles pre-perihelion, and six post-perihelion [3]. CO was enriched in Garradd while C2H2 was strongly depleted. C2H6 and CH3OH displayed abundances close to those measured for the majority of Oort cloud comets observed to date. The high fractional abundance of CO identifies comet C12009 P1 as a CO-rich comet. Spatial profiles revealed notable differences among individual primary species. Given the relatively large heliocentric distance of C/2009 Pl, we explored the effect of water not being fully sublimated within our field of view and we identi$, the "missing" water fraction needed to reconcile the retrieved abundance ratios with the mean values found for "organics-normal" comets.

It is relatively easy to identify the reservoir from which a given comet was ejected. But dynamical models demonstrate that the main cometary reservoirs (Kuiper Belt, Oort Cloud) each contain icy bodies that formed in a range of environments in the protoplanetary disk, and the Oort Cloud may even contain bodies that formed in disks of sibling stars in the Sun s birth cluster. The cometary nucleus contains clues to the formative region(s) of its individual components. The composition of ices and rocky grains reflect a range of processes experienced by material while on the journey from the natal interstellar cloud core to the cometary nucleus. For that reason, emphasis is placed on classifying comets according to their native ices and dust (rather than orbital dynamics). Mumma & Charnley [1] reviewed the current status of taxonomies for comets and relation to their natal 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.

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.

For many years we have been developing the ability, through high-resolution spectroscopy targeting ro-vibrational emission in the approximately 3 - 5 micrometer region, to quantify a suite of (approximately 10) parent volatiles in comets using quantum mechanical fluorescence models. Our efforts are ongoing and our latest includes methanol (CH3OH). This is unique among traditionally targeted species in having lacked sufficiently robust models for its symmetric (v(sub 3) band) and asymmetric (v(sub 2) and v(sub 9) bands) C-H3 stretching modes, required to provide accurate predicted intensities for individual spectral lines and hence rotational temperatures and production rates. This has provided the driver for undertaking a detailed empirical study of line intensities, and has led to substantial progress regarding our ability to interpret CH3OH in comets. The present study concentrates on the spectral region from approximately 2970 - 3010 per centimeter (3.367 - 3.322 micrometer), which is dominated by emission in the (v(sub 7) band of C2H6 and the v(sub 2) band of CH3OH, with minor contributions from CH3OH (v(sub 9) band), CH4 (v(sub 3)), and OH prompt emissions (v(sub 1) and v(sub 2)- v(sub 1)). Based on laboratory jet-cooled spectra (at a rotational temperature near 20 K)[1], we incorporated approximately 100 lines of the CH3OH v(sub 2) band, having known frequencies and lower state rotational energies, into our model. Line intensities were determined through comparison with several comets we observed with NIRSPEC at Keck 2, after removal of continuum and additional molecular emissions and correcting for atmospheric extinction. In addition to the above spectral region, NIRSPEC allows simultaneous sampling of the CH3OH v(sub 3) band (centered at 2844 per centimeter, or 3.516 micrometers and several hot bands of H2O in the approximately 2.85 - 2.9 micrometer region, at a nominal spectral resolving power of approximately 25,000 [2]. Empirical g-factors for v(sub 2) lines were based on the production rate as determined from the v(sub 3) Q-branch intensity; application to comets spanning a range of rotational temperatures (approximately 50 - 90 K) will be reported. This work represents an extension of that presented for comet 21P/Giacobini-Zinner at the 2010 Division for Planetary Sciences meeting [3]. Our empirical study also allows for quantifying CH3OH in comets using IR spectrometers for which the v(sub 3) and v(sub 2) bands are not sampled simultaneously, for example CSHELL/NASA IRTF or CRIRES/VLT.

We acquired high resolution near-infrared spectra of comet 103P/Hartley-2 with NIRSPEC at the W. M. Keck Observatory and CRIRES at the ESO VLT, emphasizing primary volatiles before, during, and after the comet's close approach to Earth (July-December 2010; R(sub h) =1.62 right arrow 1.26 AU). We will present the mixing ratios for trace volatiles (C2H6, HCN, CH3OH, etc.), their rotational temperatures, and their spatial distributions in the coma both along the polar jet (UT 19.5 October) and nearly orthogonal to the jet (UT 22.5 October).

We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet lO3P/Hartley-2 using high dispersion infrared spectroscopy. We quantified the long- and short-term behavior of volatile release over a three-month interval that encompassed the comet's close approach to Earth, its perihelion passage, and flyby of the comet by the Deep Impact spacecraft during the EPOXI mission. We present production rates for individual species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates. The production rates for water, ethane, HCN, and methanol vary in a manner consistent with independent measures of nucleus rotation, but mixing ratios for HCN, C2H6, & CH3OH are independent of rotational phase. Our results demonstrate that the ensemble average composition of gas released from the nucleus is well defined, and relatively constant over the three-month interval (September 18 through December 1,7). If individual vents vary in composition, enough diverse vents must be active simultaneously to approximate (in sum) the bulk composition of the nucleus. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps, and from the nucleus, and provide insights into the driver for the cyanogen (CN) polar jet. The spatial distributions of C2H6 & HCN along the near-polar jet (UT 19.5 October) and nearly orthogonal to it (UT 22.5 October) are discussed relative to the origin of CN. The ortho-para ratio (OPR) of water was 2.85 +/- 0.20; the lower bound (2.65) defines T(sub spin) > 32 K. These values are consistent with results returned from ISO in 1997 .

We report measurements of eight primary volatiles (H2O, HCN, CH4, C2H6, CH3OH, C2H2, H2CO, and NH3) and two product species (OH and NH2) in comet 103P/Hartley-2 using high dispersion infrared spectroscopy. We present production rates for individual volatiles species, their mixing ratios relative to water, and their spatial distributions in the coma on multiple dates that span the interval Sept. - Dec. 2010. The production rates vary strongly with nucleus rotation, but the mixing ratios remain constant throughout the campaign. The released primary volatiles exhibit diverse spatial properties which favor the presence of separate polar and apolar ice phases in the nucleus, establish dust and gas release from icy clumps (and also, directly from the nucleus), and provide insights into the driver for the cyanogen (CN) polar jet.