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Centaurs are minor solar system bodies with orbits transitioning between those of Trans-Neptunian Scattered Disk objects and Jupiter Family comets. 39P/Oterma is a frequently active Centaur that has recently held both Centaur and JFC classifications and was observed with the JWST NIRSpec instrument on 2022 July 27 UTC while it was 5.82 au from the Sun. For the first time, CO$_2$ gas emission was detected in a Centaur, with a production rate of Q$_{CO_2}$ = (5.96 $\pm$ 0.80) $\times$ 10$^{23}$ molecules s$^{-1}$. This is the lowest detection of CO$_2$ of any Centaur or comet. CO and H$_2$O were not detected down to constraining upper limits. Derived mixing ratios of Q$_{CO}$/Q$_{CO_2}$ $\leq$2.03 and Q$_{CO_2}$/Q$_{H_2O}$ $\geq$0.60 are consistent with CO$_2$ and/or CO outgassing playing large roles in driving the activity, but not water, and show a significant difference between the coma abundances of 29P/Schwassmann-Wachmann 1, another Centaur at a similar heliocentric distance, which may be explained by thermal processing of 39P's surface during its previous Jupiter-family comet orbit. To help contextualize the JWST data we also acquired visible CCD imaging data on two dates in July (Gemini North) and September (Lowell Discovery Telescope) 2022. Image analysis and photometry based on these data are consistent with a point source detection and an estimated effective nucleus radius of 39P in the range of $R_{nuc}= $2.21 to 2.49~km.

We present the results of a molecular survey of comet 46P/Wirtanen undertaken with the IRAM 30-m and NOEMA radio telescopes in December 2018. Observations at IRAM 30-m during the 12-18 Dec. period comprise a 2 mm spectral survey covering 25 GHz and a 1 mm survey covering 62 GHz. The gas outflow velocity and kinetic temperature have been accurately constrained by the observations. We derive abundances of 11 molecules, some being identified remotely for the first time in a Jupiter-family comet, including complex organic molecules such as formamide, ethylene glycol, acetaldehyde, or ethanol. Sensitive upper limits on the abundances of 24 other molecules are obtained. The comet is found to be relatively rich in methanol (3.4 percent relative to water), but relatively depleted in CO, CS, HNC, HNCO, and HCOOH., Comment: 35 pages, 16 figures, to be published in Astronomy & Astrophysics

We present a multi-wavelength study of comet C/2016 R2 (PanSTARRS). This comet was observed on 23-24 January 2018 with the IRAM 30m telescope, and in January to March 2018 with the Nan\c{c}ay radio telescope. Visible spectroscopy was performed in December 2017 and February 2018 with small amateur telescopes. We report on measurements of CO, CH3OH, H2CO and HCN production rates, and on the determination of the N2/CO abundance ratio. Several other species, especially OH, were searched for but not detected. The inferred relative abundances, including upper limits for sulfur species, are compared to those measured in other comets at about the same heliocentric distance of about 2.8 AU. The coma composition of comet C/2016 R2 is very different from all other comets observed so far, being rich in N2 and CO and dust poor. This suggests that this comet might belong to a very rare group of comets formed beyond the N2 ice line. Alternatively, comet C/2016 R2 (PanSTARRS) could be the fragment of a large and differentiated transneptunian object, with properties characteristic of volatile-enriched layers., Comment: 14 pages, 16 figures. Accepted for publication in Astronomy & Astrophysics

We present a summary of the campaign of remote observations that supported the European Space Agency's Rosetta mission. Telescopes across the globe (and in space) followed comet 67P/Churyumov-Gerasimenko from before Rosetta's arrival until nearly the end of mission in September 2016. These provided essential data for mission planning, large-scale context information for the coma and tails beyond the spacecraft, and a way to directly compare 67P with other comets. The observations revealed 67P to be a relatively `well behaved' comet, typical of Jupiter family comets and with activity patterns that repeat from orbit-to-orbit. Comparison between this large collection of telescopic observations and the in situ results from Rosetta will allow us to better understand comet coma chemistry and structure. This work is just beginning as the mission ends -- in this paper we present a summary of the ground-based observations and early results, and point to many questions that will be addressed in future studies., Comment: Author prepared version; final published version available at journal. 22 pages

We quantified ten parent volatiles in comet C/2009 P1 (Garradd) before perihelion, through high-dispersion infrared spectra acquired with CRIRES at ESO's VLT on UT 2011 August 07 (Rh = 2.4 AU) and September 17-21 (Rh = 2.0 AU). On August 07, water was searched but not detected at an upper limit (3{\sigma}) of 2.1 \times 10^28 s-1, while ethane was detected with a production rate of 6.1 \times 10^26 s-1 (apparent mixing ratio > 2.90%). On September 17-21, the mean production rate for water was 8.4 \times 10^28 s-1, and abundance ratios (relative to water) of detected trace species were: CO (12.51%), CH3OH (3.90%), CH4 (1.24%), C2H6 (1.01%) and HCN (0.36%). Upper limits (3{\sigma}) to abundances for four minor species were: NH3 (1.55%), C2H2 (0.13%), HDO (0.89%) and OCS (0.20%). Given the relatively large heliocentric distance, we explored the effect of water not being fully sublimated within our FOV and identified the 'missing' water fraction needed to reconcile the retrieved abundance ratios with the mean values found for "organics-normal". The individual spatial profiles of parent volatiles and the continuum displayed rather asymmetric outgassing. Indications of H2O and CO gas being released in different directions suggest different active vents and/or the possible existence of polar and apolar ice aggregates in the nucleus. The high fractional abundance of CO identifies comet C/2009 P1 as a CO-rich comet., Comment: To appear in: The Astrophysical Journal Letters (LET27048R)

We present spectral and spatial information for major volatile species in Comet 10P/Tempel 2, based on high-dispersion infrared spectra acquired on UT 2010 July 26 (heliocentric distance Rh = 1.44 AU) and September 18 (Rh = 1.62 AU), following the comet's perihelion passage on UT 2010 July 04. The total production rate for water on July 26 was (1.90 +/- 0.12) x 10^28 molecules s-1, and abundances of six trace gases (relative to water) were: CH3OH (1.58% +/- 0.23), C2H6 (0.39% +/- 0.04), NH3 (0.83% +/- 0.20), and HCN (0.13% +/- 0.02). A detailed analysis of intensities for water emission lines provided a rotational temperature of 35 +/- 3 K. The mean OPR is consistent with nuclear spin populations in statistical equilibrium (OPR = 3.01 +/- 0.18), and the (1-sigma) lower bound corresponds to a spin temperature > 38 K. Our measurements were contemporaneous with a jet-like feature observed at optical wavelengths. The spatial profiles of four primary volatiles display strong enhancements in the jet direction, which favors release from a localized vent on the nucleus. The measured IR continuum is much more sharply peaked and is consistent with a dominant contribution from the nucleus itself. The peak intensities for H2O, CH3OH, and C2H6 are offset by ~200 km in the jet direction, suggesting the possible existence of a distributed source, such as the release of icy grains that subsequently sublimed in the coma. On UT September 18, no obvious emission lines were present in our spectra, nevertheless we obtained a 3-sigma upper limit Q(H2O) < 2.86 x 10^27 molecules s-1.

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 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 17). 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 also, directly 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 \pm 0.20; the lower bound (2.65) defines Tspin > 32 K. These values are consistent with results returned from ISO in 1997., Comment: 18 pages, 3 figures, to be published in: Astrophysical Journal Letters

We measured organic volatiles (CH4, CH3OH, C2H6, H2CO), CO, and water in comet 8P/Tuttle, a comet from the Oort cloud reservoir now in a short-period Halley-type orbit. We compare its composition with two other comets in Halley-type orbits, and with comets of the "organics-normal" and "organics-depleted" classes. Chemical gradients are expected in the comet-forming region of the proto-planetary disk, and an individual comet should reflect its specific heritage. If Halley-type comets came from the inner Oort cloud as proposed, we see no common characteristics that could distinguish such comets from those that were stored in the outer Oort cloud., Comment: 14 pages, including 1 figure and 2 Tables

We report measurements of eight native (i.e., released directly from the comet nucleus) volatiles (H2O, HCN, CH4, C2H2, C2H6, CO, H2CO, and CH3OH) in comet 8P/Tuttle using NIRSPEC at Keck 2. Comet Tuttle reveals a truly unusual composition, distinct from that of any comet observed to date at infrared wavelengths. The prominent enrichment of methanol relative to water contrasts the depletions of other molecules, especially C2H2 and HCN. We suggest that the nucleus of 8P/Tuttle may contain two cometesimals characterized by distinct volatile composition. The relative abundances C2/CN, C2/OH, and CN/OH in 8P/Tuttle (measured at optical/near-UV wavelengths) differ substantially from the mixing ratios of their potential parents (C2H2/HCN, C2H2/H2O, and HCN/H2O) found in this work. Based on this comparison, our results do not support C2H2 and HCN being the principal precursors for respectively C2 and CN in Tuttle. The peculiar native composition observed in 8P/Tuttle (compared to other comets) provides new strong evidence for chemical diversity in the volatile materials stored in comet nuclei. We discuss the implications of this diversity for expected variations in the deuterium enrichment of water among comets., Comment: Accepted for Astrophysical Journal Letters

We used iSHELL, the powerful high-resolution ( λ/Δλ~ 40,000) cross-dispersed IR spectrograph at the NASA-IRTF to measure the native ice composition and outgassing of moderately bright, long-period comet C/2018 Y1 (Iwamoto) (hereafter Y1) within weeks of its discovery. We measured production rates for H2O, and production rates and abundance ratios relative to H2O for eight trace molecules, including the most complete measure of cometary CH4 achieved to date. Compared with mean abundances measured among comets, our study revealed enriched CH3OH and C2H6 yet depleted CO and C2H2, perhaps indicating highly efficient H- atom addition on interstellar grains prior to their incorporation into the nucleus. The combined high spectral resolving power and broad spectral coverage of iSHELL allowed characterizing cometary composition using only three instrument settings, and its long-slit coverage allowed comparing the spatial distributions of molecular emissions and dust continuum.

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.

Volatile production rates, relative abundances, rotational temperatures, and spatial distributions in the coma were measured in C/2012 S1 (ISON) using long-slit high-dispersion (lambda/delta lambda approximately 2.5 times 10 (sup 4)) infrared spectroscopy as part of a worldwide observing campaign. Spectra were obtained on Universal Time 2013 October 26 and 28 with NIRSPEC (Near Infrared Spectrometer) at the W.M. Keck Observatory, and Universal Time 2013 November 19 and 20 with CSHELL (Cryogenic Echelle Spectrograph) at the NASA IRTF (Infrared Telescope Facility). H2O was detected on all dates, with production rates increasing markedly from (8.7 plus or minus 1.5) times 10 (sup 27) molecules per second on October 26 (Heliocentric Distance = 1.12 Astronomical Units) to (3.7 plus or minus 0.4) times 10 (sup 29) molecules per second on November 20 (Heliocentric Distance = 0.43 Astronomical Units). Short-term variability of H2O production is also seen as observations on November 19 show an increase in H2O production rate of nearly a factor of two over a period of about 6 hours. C2H6, CH3OH and CH4 abundances in ISON (International Scientific Optical Network) are slightly depleted relative to H2O when compared to mean values for comets measured at infrared wavelengths. On the November dates, C2H2, HCN and OCS abundances relative to H2O appear to be within the range of mean values, whereas H2CO and NH3 were significantly enhanced. There is evidence that the abundances with respect to H2O increased for some species but not others between October 28 (Heliocentric Distance = 1.07 Astronomical Units) and November 19 (Heliocentric Distance = 0.46 Astronomical Units). The high mixing ratios of H2CO to CH3OH and C2H2 to C2H6 on November 19, and changes in the mixing ratios of some species with respect to H2O between October 28 to November 19, indicates compositional changes that may be the result of a transition from sampling radiation-processed outer layers in this dynamically new comet to sampling more pristine natal material as the outer processed layer was increasingly eroded and the thermal wave propagated into the nucleus as the comet approached perihelion for the first time. On November 19 and 20, the spatial distribution for dust appears asymmetric and enhanced in the antisolar direction, whereas spatial distributions for volatiles (excepting CN) appear symmetric with their peaks slightly offset in the sunward direction compared to the dust. Spatial distributions for H2O, HCN, C2H6, C2H2, and H2CO on November 19 show no definitive evidence for significant contributions from extended sources; however, broader spatial distributions for NH3 and OCS may be consistent with extended sources for these species. Abundances of HCN and C2H2 on November 19 and 20 are insufficient to account for reported abundances of CN and C2 in ISON near this time. Differences in HCN and CN spatial distributions are also consistent with HCN as only a minor source of CN in ISON on November 19 as the spatial distribution of CN in the coma suggests a dominant distributed source that is correlated with dust and not volatile release. The spatial distributions for NH3 and NH2 are similar, suggesting that NH3 is the primary source of NH2 with no evidence of a significant dust source of NH2; however, the higher production rates derived for NH3 compared to NH2 on November 19 and 20 remain unexplained. This suggests a more complete analysis that treats NH2 as a distributed source and accounts for its emission mechanism is needed for future work.

We report observations at millimeter and submillimeter wavelengths of comet C/2009 P1 (Garradd) from 2011 December 28 to 2012 April 24, using the Arizona Radio Observatory submillimeter telescope (SMT) and the James Clerk Maxwell Telescope (JCMT). Garradd is a dynamically young long-period comet from the Oort Cloud, with a periodicity of 127,000 years, that reached perihelion on 2011 December 23 (at Heliocentric distance (Rh) = 1.55 Astronomical Units and delta = 20.1 Astronomical Units ) and made its closest approach to the Earth on 2012 March 05 (at Heliocentric distance (Rh) = 1.84 Astronomical Units and delta = 1.26 Astronomical Units). We obtained gas production rates, and molecular abundances relative to water for HCN, ortho-H2CO, CS, CO and CH3OH. A rotational temperature, T (sub rot) approximately equal to 50 degrees Kelvin, was determined by observing multiple methanol lines with the JCMT. By averaging the abundance ratio relative to water from the SMT and the JCMT we derive: CO: 7.03 plus or minus 1.84 percent, HCN: 0.04 plus or minus 0.01 percent, ortho H2CO: 0.14 plus or minus 0.03 percent as a parent molecule (and 0.28 plus or minus 0.06 percent as an extended source), CS: 0.03 plus or minus 0.01 percent and CH3OH: 3.11 for a range from plus 1:86 to minus 0.51 percent. We concluded that Garradd is normal in CH3OH, depleted in HCN, ortho-H2CO and CS and slightly enriched in CO with respect to typically observed cometary mixing ratios. We also studied the temporal evolution of HCN and CO and find that the production of HCN has a trend similar to water (but with short-term variation), with a decrease after perihelion, while that of CO shows contrary behavior: remaining constant or increasing after perihelion.

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.

Infrared spectra of Comet 2lP/Giacobini-Zinner (hereafter 2IP/GZ) were obtained using NIRSPEC at Keck II on UT 2005 June 03, approximately one month before perihelion, that simultaneously measured H2O, C2H6, and CH3OH. For H2O, the production rate of 3.8 x 10(exp 28) molecules / S was consistent with that measured during other apparitions of 21P/GZ retrieved from optical, infrared, and mm-wavelength observations. The water analysis also provided values for rotational temperature (T(sub rot) = 55(epx +3) /-.2 K) and the abundance ratio of ortho- and para-water (3.00 +/-0.15, implying a spin temperature exceeding 50 K). Six Q-branches in the V7 band of C2H6 provided a production rate (5.27 +/- 0.90 x 10(exp 25)/S) that corresponded to an abundance ratio of 0.139 +/- 0.024 % relative to H2O, confirming the previously reported strong depletion of C2H6 from IR observations during the 1998 apparition, and in qualitative agreement with the depletion in C2 known from optical studies. For CH30H, we applied our recently published ab initia model for the v3 band to obtain a rotational temperature (48(exp + 10) / -7 K) consistent with that obtained for H2O. In addition we applied a newly developed empirical model for the CH30H v2 band, and obtained a production rate consistent with that obtained from the v3 band. Combining results from both v2 and v3 bands provided a production rate (47.5 +/- 4.4 x 10(exp 25) / S) that corresponded to an abundance ratio of 1.25 +/- 0.12 % relative to H2O in 21P/GZ. Our study provides the first measure of primary volatile production rates for any Jupiter family comet over multiple apparitions using high resolution IR spectroscopy.

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.

Methanol (CH3OH) radiates efficiently at infrared wavelengths, dominating the C-H stretching region in comets, yet inadequate quantum-mechanical models have imposed limits on the practical use of its emission spectra. Accordingly, we constructed a new line-by-line model for the 3 fundamental band of methanol at 2844 / cm (3.52 micron) and applied it to interpret cometary fluorescence spectra. The new model permits accurate synthesis of line-by-line spectra for a wide range of rotational temperatures, ranging from 10 K to more than 400 K.We validated the model by comparing simulations of CH3OH fluorescent emission with measured spectra of three comets (C/2001 A2 LINEAR, C/2004 Q2 Machholz and 8P/Tuttle) acquired with high-resolution infrared spectrometers at high-altitude sites. The new model accurately describes the complex emission spectrum of the nu3 band, providing distinct rotational temperatures and production rates at greatly improved confidence levels compared with results derived from earlier fluorescence models. The new model reconciles production rates measured at infrared and radio wavelengths in C/2001 A2 (LINEAR). Methanol can now be quantified with unprecedented precision and accuracy in astrophysical sources through high-dispersion spectroscopy at infrared wavelengths

We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. Based on a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We then retrieved water and D/H in the atmospheres of Mars, comet C/2007 WI, and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

We developed a modern methodology to retrieve water (H2O) and deuterated water (HDO) in planetary and cometary atmospheres, and constructed an accurate spectral database that combines theoretical and empirical results. On the basis of a greatly expanded set of spectroscopic parameters, we built a full non-resonance cascade fluorescence model and computed fluorescence efficiencies for H2O (500 million lines) and HDO (700 million lines). The new line list was also integrated into an advanced terrestrial radiative transfer code (LBLRTM) and adapted to the CO2 rich atmosphere of Mars, for which we adopted the complex Robert-Bonamy formalism for line shapes. We retrieved water and D/H in the atmospheres of Mars, comet C/2007 W1 (Boattini), and Earth by applying the new formalism to spectra obtained with the high-resolution spectrograph NIRSPEC/Keck II atop Mauna Kea (Hawaii). The new model accurately describes the complex morphology of the water bands and greatly increases the accuracy of the retrieved abundances (and the D/H ratio in water) with respect to previously available models. The new model provides improved agreement of predicted and measured intensities for many H2O lines already identified in comets, and it identifies several unassigned cometary emission lines as new emission lines of H2O. The improved spectral accuracy permits retrieval of more accurate rotational temperatures and production rates for cometary water.

We measured the chemical composition of Comet C/2007 W1 (Boattini) using the long-slit echelle grating spectrograph at Keck-2 (NIRSPEC) on 2008 July 9 and 10. We sampled 11 volatile species (H2O, OH*, C2H6, CH3OH, H2CO, CH4, HCN, C2H2, NH3, NH2, and CO), and retrieved three important cosmogonic indicators: the ortho-para ratios of H2O and CH4, and an upper-limit for the D/H ratio in water. The abundance ratios of almost all trace volatiles (relative to water) are among the highest ever observed in a comet. The comet also revealed a complex outgassing pattern, with some volatiles (the polar species H2O and CH3OH) presenting very asymmetric spatial profiles (extended in the anti-sunward hemisphere), while others (e.g., C2H6 and HCN) showed particularly symmetric profiles. We present emission profiles measured along the Sun-comet line for all observed volatiles, and discuss different production scenarios needed to explain them. We interpret the emission profiles in terms of release from two distinct moieties of ice, the first being clumps of mixed ice and dust released from the nucleus into the sunward hemisphere. The second moiety considered is very small grains of nearly pure polar ice (water and methanol, without dark material or apolar volatiles). Such grains would sublimate only very slowly, and could be swept into the anti-sunward hemisphere by radiation pressure and solar-actuated non-gravitational jet forces, thus providing an extended source in the anti-sunward hemisphere.

Earth- and space-based observations provide synergistic information for space mission encounters by providing data over longer timescales. at different wavelengths and using techniques that are impossible with an in situ flyby. We report here such observations in support of the EPOXI spacecraft flyby of comet 103P (Hartley 2. The nucleus is small and dark, and exhibited a very rapidly changing rotation period. Prior to the onset of activity, the period was approximately 16.4 hr. Starting in 2010 August the period changed from 16.6 hr to near 19 hr in December. With respect to dust composition, most volatiles and carbon and nitrogen isotope ratios, the comet is similar to other Jupiter-family comets. What is unusual is the dominance of CO2-driven activity near perihelion, which likely persists out to aphelion. Near perihelion the comet nucleus was surrounded by a large halo of water-ice grains that contributed significantly to the total water production.

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.

Comets contain relatively well preserved icy material remaining from the epoch of Solar System formation, however the extent to which these ices are modified from their initial state remains a fundamental question in cometary science. As a comet approaches the Sun, sublimation of the ices contained in its nucleus (termed " native ices") releases parent volatiles into the coma, where they can be measured spectroscopically. One means of assessing the degree to which interstellar ices were processed prior to their incorporation into cometary nuclei is to measure the relative abundances of chemically-related parent volatiles. For example, formation of C2H6 by hydrogen atom addition (e.g., to C2H2) on surfaces of ice-mantled grains was proposed to explain the high C2H6 to CH4 abundance observed in C/1996 B2 (Hyakutake) [1]. The large C2H6/CH4 abundance ratios measured universally in comets, compared with those predicted by gas phase production of C2H6, establishes H-atom addition as an important and likely ubiquitous process. CO should also be hydrogenated on grain surfaces. Laboratory irradiation experiments on interstellar ice analogs indicate this to require very low temperatures (T approx. 10-25 K), the resulting yields of H2CO and CH3OH being highly dependent both on hydrogen density (i.e., fluence) and on temperature ([2],[3]). This relatively narrow range in temperature reflects a lack of mobility below 8-10 K on the one hand, and reduced sticking times for H-atoms as grain surfaces are warmed above 20 K on the other. The relative abundances of these three chemically-related molecules in comets provides one measure of the efficiency of H-atom addition to CO on pre-cometary grains (Fig. 1).

Ozone and water are key species for understanding the stability and evolution of Mars atmosphere; they are closely linked (along with CO, H, OH, and O) through photochemistry. Photolysis of water produces the OH radical (thought to catalyze reformation of CO2 from CO and O2) and atomic hydrogen (which reacts with O3 forming OH and O2). Atomic hydrogen also reacts with O2 (forming HO2), thereby reducing the amount of O2 available to reform O3 from collisions between O and O2. Hence ozone and water should be anti-correlated on Mars. Photolysis of O3 produces O2(a(sup 1) delta g) with 90% efficiency, and the resulting emission band system near 1.27 mm traces the presence and abundance of ozone. This approach was initially used to study ozone on Earth and then applied to Mars. In 1997, we measured several lines of the O2(a(sup 1) delta g) emission using CSHELL at the NASA IRTF; the O2(a(sup 1) delta g) state is also quenched by collisions with CO2. This quenching dominates at lower altitudes so that the detected emissions are used to detect ozone column densities above ~20 km. The slit was positioned N-S along Mars' central meridian resulting in a one-dimensional map of ozone. Nearly simultaneous maps may be made of water using CSHELL by detecting the v1 fundamental band of HDO near 3.67 microns and using the D/H ratio for Mars. This technique was used by DiSanti and Mumma. With CSHELL, measurements for both O2(a(sup 1) delta g) emissions and HDO absorptions can be made during the day or night. Since January, 1997, we have repeated these measurements at different times during the Martian year. For all of these dates, we have positioned the slit N-S along the central meridian; for some of these dates, we have also stepped the slit across the planet at 1 arc-sec intervals generating a 2-dimensional map. We have also positioned the slit E-W on Mars thus providing diurnal variations of ozone and water along the slit.

Ethane and carbon monoxide were detected in a short-period comet of probable Kuiper belt origin. Ethane is substantially less abundant compared with Hyakutake and Hale-Bopp, two comets from the giant-planets region of the solar nebula, suggesting a heliocentric gradient in ethane in pre-cometary ices. It is argued that processing by X-rays from the young sun may be responsible.

The saturated hydrocarbons ethane (C2H6) and methane (CH4) along with carbon monoxide (CO) and water (H2O) were detected in comet C/1996 B2 Hyakutake with the use of high-resolution infrared spectroscopy at the NASA Infrared Telescope Facility on Mauna Kea, Hawaii. The inferred production rates of molecular gases from the icy, cometary nucleus (in molecules per second) are 6.4 X 10(26) for C2H6, 1.2 X 10(27) for CH4, 9.8 X 10(27) for CO, and 1.7 X 10(29) for H2O. An abundance of C2H6 comparable to that of CH4 implies that ices in C/1996 B2 Hyakutake did not originate in a thermochemically equilibrated region of the solar nebula. The abundances are consistent with a kinetically controlled production process, but production of C2H6 by gas-phase ion molecule reactions in the natal cloud core is energetically forbidden. The high C2H6/CH4 ratio is consistent with production of C2H6 in icy grain mantles in the natal cloud, either by photolysis of CH4-rich ice or by hydrogen-addition reactions to acetylene condensed from the gas phase.

The design of an IR mapping spectrometer that exceeds all the criteria of the Pluto Fast Flyby Mission will be presented. The instrument has a mass of approximately 1700 g and uses less than 4 W of power. The design concept is based on an f/3 spectrograph using an aberration-corrected concave holographic grating. Up to four spectral regions can be covered simultaneously by dividing the grating into two to four sections, each imaging the entrance slit on a different area of the array. The spectrography will be fed by a lightweight 5 in. f/3 telescope based on SDIO precepts. In order to provide spectroscopic access to the fundamental molecule frequencies, an extended-range NICMOS array to approximately 3.5 microns and an InSb array going to 5.8 microns will be considered.

Four color maps of Arp 146 are given. The structure and color of the ring galaxy and its companion show evidence of a bridge of material between the companion and the remnant nucleus of the original galaxy now forming the ring. Broad band spatial coverage clearly defines regions of starburst occurrence.