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We present high-resolution infrared spectroscopic measurements of the ecliptic comet 2P/Encke, observed on 4-6 Nov. 2003 during its close approach to the Earth, using the Near Infrared Echelle Spectrograph on the Keck II telescope. We present flux-calibrated spectra, production rates, and mixing ratios for H2O, CH3OH, HCN, H2CO, C2H2, C2H6, CH4 and CO. Comet 2P/Encke is a dynamical end-member among comets because of its short period of 3.3 years. Relative to "organics-normal" comets, we determined that 2PlEncke is depleted in HCN, H2CO, C2H2, C2H6, CH4 and CO, but it is enriched in CH3OH. We compared mixing ratios of these organic species measured on separate dates, and we see no evidence of macroscopic chemical heterogeneity in the nucleus of 2P/Encke, however, this conclusion is limited by sparse temporal sampling. The depleted abundances of most measured species suggest that 2P/Encke may have formed closer to the young Sun, before its insertion to the Kuiper belt, compared with "organics-normal" comets - as was previously suggested for other depleted comets (e.g. C/1999 S4 (LINEAR)). We measured very low rotational temperatures of 20 - 30 K for H2O, CH3OH and HCN in the near nucleus region of 2P/Encke, which correlate with one of the lowest cometary gas production rates (approx. 2.6 x 10(exp 27) molecules/s) measured thus far in the infrared. This suggests that we are seeing the effects of more efficient radiative cooling, insufficient collisional excitation, and/or inefficient heating by fast H-atoms (and icy grains) in the observed region of the coma. Its extremely short orbital period, very low gas production rate, and classification as an ecliptic comet, make 2PlEncke an important addition to our growing database, and contribute significantly to the establishment of a chemical taxonomy of comets.

This paper presents long-slit spectra of H2O emission from the inner coma of Comet 103P/Hartley 2, acquired with NIRSPEC/Keck 2 during the comet’s close approach to Earth in 2010. On UT 19.6 October 2010 the slit was oriented nearly orthogonal to the projected (in the plane of the sky) Sun–comet line, and the H2O rotational temperature and column density showed similar spatial distributions as a function of projected distance from the nucleus. On UT 22.5 October, the slit was oriented along the Sun–comet line, and the rotational temperatures revealed pronounced asymmetry while the column densities were nearly symmetric about the nucleus. We suggest this dichotomy reflects two qualitatively different mechanisms of volatile release, which introduce distinct rotational distributions in the sublimated material. Future modeling can test this hypothesis. We also report new retrievals of water nuclear spin species (ortho, para) in this comet, and we present the ortho-to-para ratio (OPR) for various projected nucleocentric distances. Our most precise individual measurement is OPR = 2.59 ± 0.13, corresponding to a nuclear spin temperature (Tspin) of 31 ± 3 K. A weighted mean of five independent measurements provides OPR = 2.79 ± 0.13 ( T spin = 37 - 4 + 8 K ). Hartley 2 is the first comet for which the OPR has been measured in multiple apparitions. Our values (in 2010) are in good agreement with those obtained two apparitions earlier by the Infrared Space Observatory. Since the comet lost a substantial amount of material between 1998 and 2010, we see no evidence for variation of the OPR with depth in the nucleus. Further discussion of the advantages, assumptions, and biases introduced by various approaches when quantifying nuclear spin species (observing techniques, models and model parameters, sources of uncertainty) would likely aid in interpreting the OPRs measured in cometary volatiles.

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., Accepted for Publication in Icarus (27 pages, 4 tables, 4 figures)

We report a sensitive search for deuterated water (HDO) in comet 8P/Tuttle using high-resolution spectroscopy at infrared (IR) wavelengths. The deuterium enrichment of cometary water is one of the most important cosmogonic indicators in comets. The ratio preserves information about the conditions under which comet material formed, and tests the possible contribution of comets in delivering water for Earth's oceans. Water (H2O) and HDO were sampled in comet 8P/Tuttle from 2008 January 27 to 2008 February 3 using the new IR spectrometer (Cryogenic Infrared Echelle Spectrograph) at the 8.2 m Antu telescope of the Very Large Telescope Observatory atop Cerro Paranal, Chile. Twenty-three lines of HDO were sampled near 3.7 μm, leading to a production rate of 4.73 ± 1.68 × 1025 s–1. Combining this value with the H2O production rate of 5790 ± 250 × 1025 s–1 provides a formal value of = 4.09 ± 1.45 × 10–4 in comet 8P/Tuttle. This value is larger by a factor of 2.62 ± 0.93 than Vienna Standard Mean Ocean Water, and is comparable to enrichment factors measured for three other Oort cloud comets. The technique described here provides unprecedented sensitivities, ultimately permitting us to routinely measure this prime cosmogonic indicator, even in comets having relatively modest gas production rate like 8P/Tuttle.

We report production rates for H2O and eight trace molecules (CO, C_2H_6, CH_4, CH_3OH, NH_3, H_2CO, HCN, C_2H_2) in the dynamically new, Sun-grazing Comet C/2012 S1 (ISON), using high-resolution spectroscopy at Keck II and the NASA IRTF on 10 pre-perihelion dates encompassing heliocentric distances R_h = 1.21–0.34 AU. Measured water production rates spanned two orders of magnitude, consistent with a long-term heliocentric power law Q(H_2O) ∝ R_h^(-3.1±0.1). Abundance ratios for CO, C_2H_6, and CH_4 with respect to H_2O remained constant with R_h and below their corresponding mean values measured among a dominant sample of Oort Cloud comets. CH_3OH was also depleted for R_h > 0.5 AU, but was closer to its mean value for R_h ≤ 0.5 AU. The remaining four molecules exhibited higher abundance ratios within 0.5 AU: for R_h > 0.8 AU, NH_3 and C_2H_2 were consistent with their mean values while H_2CO and HCN were depleted. For R_h < 0.5 AU, all four were enriched, with NH_3, H_2CO, 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. NH_3 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 NH_2/H_2O at 0.83 AU was close to the "typical" NH/OH from optical wavelengths, but was higher within 0.5 AU. Establishing its production rate and testing its parentage (e.g., NH_3) require modeling of coma outflow.

Infrared emission from hydroxyl has been observed in several comets via high-resolution infrared spectroscopy. The principal excitation mechanism for this emission is single-step photolysis of H2O, terminating in OH fragments that are both vibrationally and rotationally excited. Recently reported comet data provide quantitative measures of the rotational distribution of OH*[X2Π; v' = 1] for J' < 17.5. The measured distributions of relative g-factors for OH "prompt" emission, and especially the ratios of the Π(A'') and Π(A') Λ-doubling components, are remarkably similar for comets C/2000 WM1 (LINEAR) and C/2004 Q2 (Machholz). We discuss how these results complement ab initio theoretical studies of water dissociation and those done in terrestrial laboratories.

We present high-dispersion infrared spectra of hydroxyl (OH) in comets C/2000 WM1 (LINEAR) and C/2004 Q2 (Machholz), acquired with the Near Infrared Echelle Spectrograph at the Keck Observatory atop Mauna Kea, Hawaii. Most of these rovibrational transitions result from photodissociative excitation of H_2O giving rise to OH "prompt" emission. We present calibrated emission efficiencies (equivalent g-factors, measured in OH photons s^(-1) [H_2O molecule]^(-1)) for more than 20 OH lines sampled in these two comets. The OH transitions analyzed cover a broad range of rotational excitation. This infrared database for OH can be used in two principal ways: (1) as an indirect tool for obtaining water production in comets simultaneously with the production of other parent volatiles, even when direct detections of H_2O are not available; and (2) as an observational constraint to models predicting the rotational distribution of rovibrationally excited OH produced by water photolysis.

Formaldehyde (H2CO) was observed in comet C/2002 T7 (LINEAR) with spectral resolving power k/� k � 2.5 ; 10 4 using the Cryogenic Echelle Spectrometer (CSHELL) at the NASA Infrared Telescope Facility, on UT 2004 May 5, 7, and 9. The observations, which sampled emission in the � 1 and � 5 rovibrational bands between 3.53 and 3.62 � m, represent the first spectrally resolved detection, at infrared wavelengths, of monomeric H2CO spanning a range of rotational energies. A comparison of measured line intensities with an existing fluorescence model permitted extraction of rotational temperatures and production rates. Two complementary approaches were used: (1)acorrelationanalysisthatprovidedadirectglobalcomparisonoftheobservedcometaryemissionswiththemodel and (2) an excitation analysis that provided a robust line-by-line comparison. Our results validate the fluorescence model. The overall correlation coefficient was near or above 0.9 in our two principal grating settings. The excitation analysis provided accurate measures of rotational excitation (rotational temperature) on all three dates, with retrieved values of Trot clustering near 100 K. Through simultaneous measurement of OH prompt emission, which we use as a proxy for H2O, we obtained native production rates and mixing ratios for H2CO. The native production of H2CO varied from day to day, but its abundance relative to H2O, Xnative, remained approximately constant within the errors, which may suggest an overall homogeneous composition of the nucleus. We measured a mean mixing ratio Xnative = (0.79 � 0.09) ; 10 � 2 for the three dates. Subject headingg astrochemistry — comets: individual (C/2002 T7 (LINEAR)) — infrared: solar system Online material: color figures

We obtained high-resolution ( λ / Δ λ ∼ 25 , 000 ) spectra of Comet C/1999 H1 (Lee) on UT 1999 August 19.6 and 21.6 using the cross-dispersed Near InfraRed SPECtrometer (NIRSPEC) at the Keck Observatory atop Mauna Kea, HI. Here we present spectra of Comet Lee between 2.874 and 3.701 μm (3479–2702 cm−1) representing the most complete high-resolution infrared survey of a comet to date in this wavelength region. Using published line lists and laboratory spectra we have identified 444 of the 545 distinct emission features present in these spectra. We have tabulated the rest frequencies, assignments, relative intensities, and signal-to-noise ratios of all detected emissions. In addition to gaining insights into the chemistry of Comet Lee, this survey provides a valuable tool for planning future high-resolution infrared observations of comets and other astronomical targets, and for retrospective comparison to existing high-resolution infrared datasets.

Water hot-band lines were detected in comets C/1999 H1 (Lee), C/1999 S4 (LINEAR), and C/2001 A2 (LINEAR) in the 2.9 � m spectral region using high-dispersion (k=� k � 2 ; 10 4 ) infrared spectroscopy with NIRSPEC at the W. M. Keck Observatory. The density of H2O emissions in this spectral region, the spectral coverage and resolution of NIRSPEC, and fluorescence models developed for these hot bands enabled the determination of H2O production rates, rotational temperatures, and ortho-to-para ratios (OPRs) in these comets. Previous studies revealed clear diversity in the volatile organic chemistries of these comets, suggesting that they may have formed in different regions of the early solar nebula. The nuclear spin temperature of H2O as derived from its OPR is another possible indicator of cometary formation temperature and region. Nuclear spin temperatures for H2O were derived on one date in comet S4 and two dates in Lee and A2. Derived spin temperatures for H2O in these comets are � 30, 30 þ15 � 6 ,a nd 23 þ4 � 3 K for S4, Lee, and A2, respectively. Measurements are consistent with a possible link between nuclear spin temperatures and volatile abundances, but studies of more comets and continued improvements in water hot-band fluorescence models are needed to more stringently test this. Subject headingg comets: general — comets: individual (C/1999 S4, C/2001 A2, Lee (C/1999 H1)) — infrared: solar system — techniques: spectroscopic

We report quantitative measurements of OH vibrational prompt emission in comets C/1999 H1 (Lee) and C/2001 A2 (LINEAR) based on high-dispersion infrared spectra acquired at the Keck Observatory atop Mauna Kea, Hawaii. Effective g-factors for four OH lines near 3046 cm-1 (in the 1-0 band) were obtained from simultaneous detections of OH and H2O. The measured spatial distribution of this OH "quadruplet" traces that of H2O, as expected if the excited OH is produced directly by water photolysis. These results establish OH prompt emission as an alternative (and convenient) proxy for water in comets. Possible limitations to the approach are discussed. Extension to other OH multiplets in the L band will permit direct comparison with theoretical models for the rotational population distribution of the free OH radicals produced by H2O photolysis in cometary atmospheres.

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 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., 18 pages, 3 figures, to be published in: Astrophysical Journal Letters

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 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.

Aims. Hydrogen cyanide (HCN) radiates effectively at infrared wavelengths in cometary atmospheres, and a new quantum-band model is needed to properly interpret high-resolution spectra. HCN spectra of comets 8P/Tuttle, C/2007 W1 (Boattini), and C/2008 Q3 (Garradd) have been recorded by our team using the high-resolution CRyogenic InfraRed Echelle Spectometer (CRIRES) at the Very Large Telescope (VLT), ultimately posing an excellent test for our newly developed model. Methods. We developed a quantum-band model for the ν1 fundamental of HCN using the latest spectroscopic parameters available and with it retrieved HCN in the above mentioned three comets. For each comet, we sampled several lines of HCN in the spectral region near 3 μm, and retrieved molecular production rates, mixing ratios, and rotational temperatures. Results. When compared to other comets, 8P/Tuttle is relatively depleted in HCN, while C/2007 W1 (Boattini) appears to be enriched and C/2008 Q3 (Garradd) normal. The spatial profile of HCN observed in 8P/Tuttle is symmetric, consistent with isotropic outgassing from the nucleus, while in comet C/2007 W1 we observed an asymmetric excess of HCN in the anti-solar direction. We investigated the HCN-CN parentage by comparing our production rate ratios (HCN/H2O) with those of CN/OH derived at optical wavelengths. In comet C/2007 W1 the two mixing ratios are comparable, while in 8P/Tuttle our derived HCN abundance is too low to support the HCN molecule as the only parent of the CN radical.

We obtained infrared spectra of Comet 21P/Giacobini-Zinner (hereafter 21P/GZ) using NIRSPEC at Keck II on UT 2005 June 3, approximately one month before perihelion, that simultaneously sampled H2O, C2H6, and CH3OH. Our production rate for H2O (3.885?? 0.074?? 1028?molecules?s?1) was consistent with that measured during other apparitions of 21P/GZ as retrieved from optical, infrared, and radio observations. Our analysis also provided values for rotational temperature (T rot?= 51?? 3?K) and the abundance ratio of ortho and para spin populations for water (OPR?= 2.99?? 0.23, implying a spin temperature exceeding 50?K). Six Q-branches in the ?7 band of C2H6 provided a production rate (5.27?? 0.90?? 1025?s?1) that corresponded to an abundance ratio of 0.136?? 0.023?? 10?2 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 of C2 known from optical studies of 21P/GZ. For CH3OH, we applied our recently published quantum model for the ?3 band to obtain a rotational temperature (48+10/?7?K) consistent with that obtained for H2O. In addition, we developed a new empirical model for the CH3OH ?2 band, based on observations of Comet 8P/Tuttle with NIRSPEC. The application of our ?2 model to 21P/GZ yielded a production rate in agreement with that obtained from the ?3 band. Combining results from both ?2 and ?3 bands provided a production rate (47.5?? 4.4??1025?s?1) that corresponded to an abundance ratio of 1.22?? 0.11?? 10?2 relative to H2O in 21P/GZ, indicating mild depletion of CH3OH. Together with observations of 21P/GZ in 1998, our study provides a measure of primary volatile production rates for this Jupiter family comet over multiple apparitions using high-resolution IR spectroscopy.