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Comets spend most of their lives at large distances from any star, during which time their interior compositions remain relatively unaltered. Cometary observations can therefore provide direct insight into the chemistry that occurred during their birth at the time of planet formation. To-date, there have been no confirmed observations of parent volatiles (gases released directly from the nucleus) of a comet from any planetary system other than our own. Here we present high-resolution, interferometric observations of 2I/Borisov, the first confirmed interstellar comet, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 15th-16th December 2019. Our observations reveal emission from hydrogen cyanide (HCN), and carbon monoxide (CO), coincident with the expected position of 2I/Borisov's nucleus, with production rates Q(HCN)=$(7.0\pm1.1)\times10^{23}$ s$^{-1}$ and Q(CO)=$(4.4\pm0.7)\times10^{26}$ s$^{-1}$. While the HCN abundance relative to water (0.06-0.16%) appears similar to that of typical, previously observed comets in our Solar System, the abundance of CO (35-105%) is among the highest observed in any comet within 2 au of the Sun. This shows that 2I/Borisov must have formed in a relatively CO-rich environment - probably beyond the CO ice-line in the very cold, outer regions of a distant protoplanetary accretion disk, as part of a population of small, icy bodies analogous to our Solar System's own proto-Kuiper Belt.

The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful tool for high-resolution mapping of comets, but the main interferometer (comprised of 50x12-m antennas) is insensitive to the largest coma scales due to a lack of very short baselines. In this work, we present a new technique employing ALMA autocorrelation data (obtained simultaneously with the interferometric observations), effectively treating the entire 12-m array as a collection of single-dish telescopes. Using combined autocorrelation spectra from 28 active antennas, we recovered extended HCN coma emission from comet C/2012 S1 (ISON), resulting in a fourteen-fold increase in detected line brightness compared with the interferometer. This resulted in the first detection of rotational emission from H^13CN in this comet. Using a detailed coma radiative transfer model accounting for optical depth and non-LTE excitation effects, we obtained an H^12CN/H^13CN ratio of 88+-18, which matches the terrestrial value of 89, consistent with a lack of isotopic fractionation in HCN during comet formation in the protosolar accretion disk. The possibility of future discoveries in extended sources using autocorrelation spectroscopy from the main ALMA array is thus demonstrated.

Vinyl cyanide (C$_2$H$_3$CN) is theorized to form in Titan's atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C$_2$H$_3$CN on Titan by Palmer et al. (2017) with the detection of three new C$_2$H$_3$CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C$_2$H$_3$CN on Titan. We present simultaneous observations of C$_2$H$_5$CN, HC$_3$N, and CH$_3$CN emission, and obtain the first (tentative) detection of C$_3$H$_8$ (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC$_3$N and C$_2$H$_5$CN, which are theorized to be short-lived in Titan's atmosphere, C$_2$H$_3$CN is most abundant over the southern (winter) pole, whereas the longer-lived CH$_3$CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan's atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C$_2$H$_3$CN and C$_2$H$_5$CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C$_2$H$_3$CN is found to be $3.03\pm0.29$ ppb, with a C$_2$H$_5$CN/C$_2$H$_3$CN abundance ratio of $2.43\pm0.26$. Our HC$_3$N and CH$_3$CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of $2.05\pm0.16$ and $1.63\pm0.02$, respectively., Comment: Accepted for publication in the Astronomical Journal

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

Observations of the sungrazing comet C/2012 S1 (ISON) were carried out using the Atacama Large Millimeter/submillimeter Array (ALMA) at a heliocentric distance of 0.58-0.54 AU (pre-perihelion) on 2013 November 16-17. Temporally resolved measurements of the coma distributions of HNC, CH$_3$OH, H$_2$CO and dust were obtained over the course of about an hour on each day. During the period UT 10:10-11:00 on Nov. 16, the comet displayed a remarkable drop in activity, manifested as a $>42$% decline in the molecular line and continuum fluxes. The H$_2$CO observations are consistent with an abrupt, $\approx50$% reduction in the cometary gas production rate soon after the start of our observations. On Nov. 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 CH$_3$OH and H$_2$CO during the Nov. 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., Comment: 9 pages. Accepted for publication in ApJ, February 2017

We present spatially and spectrally-resolved observations of CH$_3$OH emission from comet C/2012 K1 (PanSTARRS) using The Atacama Large Millimeter/submillimeter Array (ALMA) on 2014 June 28-29. Two-dimensional maps of the line-of-sight average rotational temperature ($T_{rot}$) were derived, covering spatial scales $0.3''-1.8''$ (corresponding to sky-projected distances $\rho\sim500$-2500 km). The CH$_3$OH column density distributions are consistent with isotropic, uniform outflow from the nucleus, with no evidence for extended sources of CH$_3$OH in the coma. The $T_{rot}(\rho)$ radial profiles show a significant drop within a few thousand kilometers of the nucleus, falling from about 60 K to 20 K between $\rho=0$ and 2500 km on June 28, whereas on June 29, $T_{rot}$ fell from about 120 K to 40 K between $\rho=$ 0 km and 1000 km. The observed $T_{rot}$ behavior is interpreted primarily as a result of variations in the coma kinetic temperature due to adiabatic cooling of the outflowing gas, as well as radiative cooling of the CH$_3$OH rotational levels. Our excitation model shows that radiative cooling is more important for the $J=7-6$ transitions (at 338 GHz) than for the $K=3-2$ transitions (at 252 GHz), resulting in a strongly sub-thermal distribution of levels in the $J=7-6$ band at $\rho\gtrsim1000$ km. For both bands, the observed temperature drop with distance is less steep than predicted by standard coma theoretical models, which suggests the presence of a significant source of heating in addition to the photolytic heat sources usually considered., Comment: Accepted for publication in ApJ, January 2017

The Atacama Large Millimeter/submillimeter Array (ALMA) was used to obtain measurements of spatially and spectrally resolved CH$_3$OH emission from comet C/2012 K1 (PanSTARRS) on 28-29 June 2014. Detection of 12-14 emission lines of CH$_3$OH on each day permitted the derivation of spatially-resolved rotational temperature profiles (averaged along the line of sight), for the innermost 5000 km of the coma. On each day, the CH$_3$OH distribution was centrally peaked and approximately consistent with spherically symmetric, uniform outflow. The azimuthally-averaged CH$_3$OH rotational temperature ($T_{rot}$) as a function of sky-projected nucleocentric distance ($\rho$), fell by about 40 K between $\rho=0$ and 2500 km on 28 June, whereas on 29 June, $T_{rot}$ fell by about 50 K between $\rho=$0 km and 1500 km. A remarkable ($\sim50$ K) rise in $T_{rot}$ at $\rho=$1500-2500 km on 29 June was not present on 28 June. The observed variations in CH$_3$OH rotational temperature are interpreted primarily as a result of variations in the coma kinetic temperature due to adiabatic cooling, and heating through Solar irradiation, but collisional and radiative non-LTE excitation processes also play a role., Comment: Submitted to Astronomy in Focus, Volume 1. Based on work presented at the XXIXth IAU General Assembly, August 2015

We report the first spectroscopic detection of ethyl cyanide (C$_2$H$_5$CN) in Titan's atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/submillimeter array (ALMA). The presence of C$_2$H$_5$CN in Titan's ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C$_2$H$_5$CNH$^+$. Here we report the detection of 27 rotational lines from C$_2$H$_5$CN (in 19 separate emission features detected at $>3\sigma$ confidence), in the frequency range 222-241 GHz. Simultaneous detections of multiple emission lines from HC$_3$N, CH$_3$CN and CH$_3$CCH were also obtained. In contrast to HC$_3$N, CH$_3$CN and CH$_3$CCH, which peak in Titan's northern (spring) hemisphere, the emission from C$_2$H$_5$CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C$_2$H$_5$CN. Radiative transfer models show that most of the C$_2$H$_5$CN is concentrated at altitudes 300-600 km, suggesting production predominantly in the mesosphere and above. Vertical column densities are found to be in the range (2-5)$\times10^{14}$ cm$^{-2}$., Comment: Published in 2015, ApJL, 800, L14

We present spectrally and spatially-resolved maps of HNC and HC$_3$N emission from Titan's atmosphere, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 2013 November 17. These maps show anisotropic spatial distributions for both molecules, with resolved emission peaks in Titan's northern and southern hemispheres. The HC$_3$N maps indicate enhanced concentrations of this molecule over the poles, consistent with previous studies of Titan's photochemistry and atmospheric circulation. Differences between the spectrally-integrated flux distributions of HNC and HC$_3$N show that these species are not co-spatial. The observed spectral line shapes are consistent with HNC being concentrated predominantly in the mesosphere and above (at altitudes $z\gtrsim 400$ km), whereas HC$_3$N is abundant at a broader range of altitudes ($z\approx70$-600 km). From spatial variations in the HC$_3$N line profile, the locations of the HC$_3$N emission peaks are shown to be variable as a function of altitude. The peaks in the integrated emission from HNC and the line core (upper-atmosphere) component of HC$_3$N (at $z\gtrsim300$ km) are found to be asymmetric with respect to Titan's polar axis, indicating that the mesosphere may be more longitudinally-variable than previously thought. The spatially-integrated HNC and HC$_3$N spectra are modeled using the NEMESIS planetary atmosphere code and the resulting best-fitting disk-averaged vertical mixing ratio (VMR) profiles are found to be in reasonable agreement with previous measurements for these species. Vertical column densities of the best-fitting gradient models for HNC and HC$_3$N are $1.9\times10^{13}$ cm$^{-2}$ and $2.3\times10^{14}$ cm$^{-2}$, respectively., Comment: Accepted for publication in ApJ Letters

Results are presented from the first cometary observations using the Atacama Large Millimeter/Submillimeter Array (ALMA), including measurements of the spatially-resolved distributions of HCN, HNC, H$_2$CO and dust within the comae of two comets: C/2012 F6 (Lemmon) and C/2012 S1 (ISON), observed at heliocentric distances of 1.5 AU and 0.54 AU, respectively. These observations (with angular resolution $\approx0.5''$), reveal an unprecedented level of detail in the distributions of these fundamental cometary molecules, and demonstrate the power of ALMA for quantitative measurements of the distributions of molecules and dust in the inner comae of typical bright comets. In both comets, HCN is found to originate from (or within a few hundred km of) the nucleus, with a spatial distribution largely consistent with spherically-symmetric, uniform outflow. By contrast, the HNC distributions are clumpy and asymmetrical, with peaks at cometocentric radii $\sim$500-1000~km, consistent with release of HNC in collimated outflow(s). Compared to HCN, the H$_2$CO distribution in comet Lemmon is very extended. The interferometric visibility amplitudes are consistent with coma production of H$_2$CO and HNC from unidentified precursor material(s) in both comets. Adopting a Haser model, the H$_2$CO parent scale-length is found to be a few thousand km in Lemmon and only a few hundred km in ISON, consistent with destruction of the precursor by photolysis or thermal degradation at a rate which scales in proportion to the Solar radiation flux.

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 present an analysis of high-resolution spectroscopy of several bright T Tauri stars using the VLT/CRIRES and Keck/NIRSPEC spectrographs, revealing the first detections of emission from HCN and C2H2 in circumstellar disks at near-infrared wavelengths. Using advanced data reduction techniques we achieve a dynamic range with respect to the disk continuum of ~500 at 3 microns, revealing multiple emission features of H2O, OH, HCN, and C2H2. We also present stringent upper limits for two other molecules thought to be abundant in the inner disk, CH4 and NH3. Line profiles for the different detected molecules are broad but centrally peaked in most cases, even for disks with previously determined inclinations of greater than 20 degrees, suggesting that the emission has both a Keplerian and non-Keplerian component as observed previously for CO emission. We apply two different modeling strategies to constrain the molecular abundances and temperatures: we use a simplified single-temperature LTE slab model with a Gaussian line profile to make line identifications and determine a best-fit temperature and initial abundance ratios, and we compare these values with constraints derived from a detailed disk radiative transfer model assuming LTE excitation but utilizing a realistic temperature and density structure. Abundance ratios from both sets of models are consistent with each other and consistent with expected values from theoretical chemical models, and analysis of the line shapes suggests the molecular emission originates from within a narrow region in the inner disk (R < 1 AU)., Comment: Accepted to the Astrophysical Journal

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 observed comet C/2007 N3 (Lulin) twice on UT 28 January 2009, using the UV grism of the Ultraviolet and Optical Telescope (UVOT) on board the Swift Gamma Ray Burst space observatory. Grism spectroscopy provides spatially resolved spectroscopy over large apertures for faint objects. We developed a novel methodology to analyze grism observations of comets, and applied a Haser comet model to extract production rates of OH, CS, NH, CN, C3, C2, and dust. The water production rates retrieved from two visits on this date were $6.7 \pm 0.7$ and 7.9 $\pm$ 0.7 x 1E28 molecules s-1, respectively. Jets were sought (but not found) in the white-light and `OH' images reported here, suggesting that the jets reported by Knight and Schleicher (2009) are unique to CN. Based on the abundances of its carbon-bearing species, comet Lulin is `typical' (i.e., not `depleted') in its composition.

High resolution spectra of Comet 8P/Tuttle were obtained in the frequency range 3440.6-3462.6 cm-1 on 3 January 2008 UT using CGS4 with echelle grating on UKIRT. In addition to recording strong solar pumped fluorescent (SPF) lines of H2O, the long integration time (152 miutes on target) enabled eight weaker H2O features to be assigned, most of which had not previously been identified in cometary spectra. These transitions, which are from higher energy upper states, are similar in character to the so-called 'SH' lines recorded in the post Deep Impact spectrum of comet Tempel 1 (Barber et al., 2007). We have identified certain characteristics that these lines have in common, and which in addition to helping to define this new class of cometary line, give some clues to the physical processes involved in their production. Finally, we derive an H2O rotational temperature of 62+/- K and a water production rate of (1.4+/-0.3)E28 molecules/s., Comment: Paper has been accepted for publication by MNRAS (11/06/09)

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

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.

Recent volcanic activity has long been considered a distinct possibility that would place major constraints on the evolution of Mars’ interior. Volcanic activity would result in the outgassing of sulfur-bearing species. As part of our multi-band search for active release of volcanic gases on Mars, we looked for carbonyl sulfide (OCS) at its combination band (v1 + v3) at 3.42 micrometers (2924 cm(exp -1), and sulfur dioxide (SO2) at 346.652 GHz, in two successive Mars years during its late Northern spring and mid Northern summer seasons (L(sub)s= 43 deg - 44 deg). The targeted volcanic districts, Tharsis and Syrtis Major, were observed during the two intervals, 15 Dec. 2011 to 6 Jan. 2012 in the first year, and 23 May 2014 to 12 June 2014 in the second year using the high resolution infrared spectrometer CSHELL on the NASA Infrared Telescope Facility, and the high resolution heterodyne receiver HARP at the James Clerk Maxwell Telescope atop Maunakea, Hawaii. No active release of such gases was detected, and we report 2 sigma upper limits of 1.8 ppbv and 3.1 ppbv for OCS and SO2, respectively, compared to 0.3 ppbv for SO2 (Encrenaz, T. et al. [2011] Astron. & Astrophys. 530, A37; Krasnopolsky, V.A. [2012] Icarus 217, 144-152) over the disk of Mars. Our retrieved upper limit on the SO2 outgassing rate of 156 tons/day (1.8 kg/s), corresponds to a mass rate of magma that is able to degas the SO2 of 104 kilotons/day (1200 kg/s), or 40,000 cu m/day (0.46 cu m/s). Our campaign places stringent limits on the concentration of sulfur-bearing species into the atmosphere of Mars.

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 observed the Oort cloud comet C/2014 Q2 (Lovejoy) on 2015 January 31 and February 1 and 2 at a heliocentric distance of 1.3 au and geocentric distance of 0.8 au during its approach to the Sun. Comet Lovejoy was observed with GIANO, the near-infrared high-resolution spectrograph mounted at the Nasmyth-A focus of the TNG (Telescopio Nazionale Galileo) telescope in La Palma, Canary Islands, Spain. We detected strong emissions of radical CN and water, along with many emission features of unidentified origin, across the 1-2.5 micron region. Spectral lines from eight ro-vibrational bands of H2O were detected, six of them for the first time. We quantified the water production rate [Q(H2O), (3.11+/- 0.14) x 10(exp 29)/s] by comparing the calibrated line fluxes with the Goddard full non-resonance cascade fluorescence model for H2O. The production rates of ortho-water [Q(H2O)ORTHO, (2.33+/- 0.11) x 10(exp 29)/s] and para-water [Q(H2O)PARA, (0.87+/-0.21) x 10(exp 29)/s] provide a measure of the ortho-to-para ratio (2.70+/- 0.76)). The confidence limits are not small enough to provide a critical test of the nuclear spin temperature.

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 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.

Direct sublimation of a comet nucleus surface is usually considered to be the main source of gas in the coma of a comet. However, evidence from a number of comets including the recent spectacular images of Comet 103P/Hartley 2 by the EPOXI mission indicates that the nucleus alone may not be responsible for all, or possibly at times even most, of the total amount of gas seen in the coma. Indeed, the sublimation of icy grains, which have been injected into the coma, appears to constitute an important source. We use the fully-kinetic Direct Simulation Monte Carlo model of Tenishev et al. to reproduce the measurements of column density and rotational temperature of water in Comet 73P-B/Schwassmann-Wachmann 3 obtained with a very high spatial resolution of approx. 30 km using IRCS/Subaru in May 2006. For gas released solely from the cometary nucleus at a heliocentric distance of 1 AU, modeled rotational temperatures start at 110 K close to the surface and decrease to only several tens of degrees by 10-20 nucleus radii. However, the measured decay of both rotational temperature and column density with distance from the nucleus is much slower than predicted by this simple model. The addition of a substantial (distributed) source of gas from icy grains in the model slows the decay in rotational temperature and provides a more gradual drop in column density profiles. Together with a contribution of rotational heating of water molecules by electrons, the combined effects allow a much better match to the IRCS/Subaru observations. From the spatial distributions of water abundance and temperature measured in 73P/SW3-B, we have identified and quantified multiple mechanisms of release. The application of this tool to other comets may permit such studies over a range of heliocentric and geocentric distances.

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.