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Spectrophotometry and organic matter on Iapetus. 1: Composition models

Iapetus shows a greater hemispheric albedo asymmetry than any other body in the solar system. Hapke scattering theory and optical constants measured in the laboratory are used to identify possible compositions for the dark material on the leading hemisphere of Iapetus. The materials considered are poly-HCN, kerogen, Murchison organic residue, Titan tholin, ice tholin, and water ice. Three-component mixtures of these materials are modeled in intraparticle mixture of 25% poly-HCN, 10% Murchison residue, and 65% water ice is found to best fit the spectrum, albedo, and phase behavior of the dark material. The Murchison residue and/or water ice can be replaced by kerogen and ice tholin, respectively, and still produce very good fits. Areal and particle mixtures of poly-HCN, Titan tholin, and either ice tholin or Murchison residue are also possible models. Poly-HCN is a necessary component in almost all good models. The presence of poly-HCN can be further tested by high-resolution observations near 4.5 micrometers.

Wilson, Peter D.↗

Association Reactions at Low Pressure: 5. The CH(sub 3)+/HCN System. A Final Word?

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a reexamination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion.

methyl cation↗

Hydrogen Cyanide in the Upper Troposphere: GEM-AQ Simulation and Comparison with ACE-FTS Observations

We investigate the spatial and temporal distribution of hydrogen cyanide (HCN) in the upper troposphere through numerical simulations and comparison with observations from a space-based instrument. To perform the simulations, we used the Global Environmental Multiscale Air Quality model (GEM-AQ), which is based on the threedimensional Gobal multiscale model developed by the Meteorological Service of Canada for operational weather forecasting. The model was run for the period 2004-2006 on a 1.5deg x 1.5deg global grid with 28 hybrid vertical levels from the surface up to 10 hPa. Objective analysis data from the Canadian Meteorological Centre were used to update the meteorological fields every 24 h. Fire emission fluxes of gas species were generated by using year-specific inventories of carbon emissions with 8-day temporal resolution from the Global Fire Emission Database (GFED) version 2. The model output is compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument onboard the Canadian SCISAT-1 satellite. High values of up to a few ppbv are observed in the tropics in the Southern Hemisphere; the enhancement in HCN volume mixing ratios in the upper troposphere is most prominent in October. Low upper-tropospheric mixing ratios of less than 100 pptv are mostly recorded at middle and high latitudes in the Southern Hemisphere in May-July. Mixing ratios in Northern Hemisphere peak in the boreal summer. The amplitude of the seasonal variation is less pronounced than in the Southern Hemisphere. The comparison with the satellite data shows that in the upper troposphere GEM-AQ perform7s well globally for all seasons, except at northern hi gh and middle latitudes in surnmer, where the model has a large negative bias, and in the tropics in winter and spring, where it exhibits large positive bias. This may reflect inaccurate emissions or possible inaccuracies in the emission profile. The model is able to explain most of the observed variability in the upper troposphere HCN field, includin g the interannual variations in the observed mixing ratio. A complementary comparison with daily total columns of HCN from two middle latitude ground-based stations in Northern Japan for the same simulation period shows that the model captures the observed seasonal variation and also points to an underestimation of model emissions in the Northern Hemisphere in the summer. The estimated average global emission equals 1.3 Tg N/yr. The average atmospheric burden is 0.53 Tg N, and the corresponding lifetime is 4.9 months.

Lupu, A.↗

The Evolution of Volatile Production in Comet C-2009 P1(Garradd) During its 2011-2012 Apparition

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.

Comets: individual↗

The Compositional Evolution of C/2012 S1 (ISON) from Ground-Based High-Resolution Infrared Spectroscopy as Part of a Worldwide Observing Campaign

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.

Russo, N. Dello↗

Temperature and Chemical Species Distributions in the Middle Atmosphere Observed during Titan's Late Northern Spring to Early Summer

We present a study of the seasonal evolution of Titan’s thermal field and distributions of haze, C2H2, C2H4, C2H6, CH3C2H, C3H8, C4H2, C6H6, HCN, and HC3N from March 2015 (Ls = 66°) to September 2017 (Ls = 93°) (i.e., from the last third of northern spring to early summer). We analyzed thermal emission of Titan’s atmosphere acquired by the Cassini Composite Infrared Spectrometer with limb and nadir geometry to retrieve the stratospheric and mesospheric temperature and mixing ratios pole-to-pole meridional cross sections from 5 mbar to 50 μbar (120–650 km). The southern stratopause varied in a complex way and showed a global temperature increase from 2015 to 2017 at high-southern latitudes. Stratospheric southern polar temperatures, which were observed to be as low as 120 K in early 2015 due to the polar night, showed a 30 K increase (at 0.5 mbar) from March 2015 to May 2017 due to adiabatic heating in the subsiding branch of the global overturning circulation. All photochemical compounds were enriched at the south pole by this subsidence. Polar cross sections of these enhanced species, which are good tracers of the global dynamics, highlighted changes in the structure of the southern polar vortex. These high enhancements combined with the unusually low temperatures (<120 K) of the deep stratosphere resulted in condensation at the south pole between 0.1 and 0.03 mbar (240–280 km) of HCN, HC3N, C6H6 and possibly C4H2 in March 2015 (Ls = 66°). These molecules were observed to condense deeper with increasing distance from the south pole. At high-northern latitudes, stratospheric enrichments remaining from the winter were observed below 300 km between 2015 and May 2017 (Ls = 90°) for all chemical compounds and up to September 2017 (Ls = 93°) for C2H2, C2H4, CH3C2H, C3H8, and C4H2. In September 2017, these local enhancements were less pronounced than earlier for C2H2, C4H2, CH3C2H, HC3N, and HCN, and were no longer observed for C2H6 and C6 H6, which suggests a change in the northern polar dynamics near the summer solstice. These enhancements observed during the entire spring may be due to confinement of this enriched air by a small remaining winter circulation cell that persisted in the low stratosphere up to the northern summer solstice, according to predictions of the Institut Pierre Simon Laplace Titan Global Climate Model (IPSL Titan GCM). In the mesosphere we derived a depleted layer in C2H2, HCN, and C2H6 from the north pole to mid-southern latitudes, while C4H2, C3H4, C2H4, and HC3N seem to have been enriched in the same region. In the deep stratosphere, all molecules except C2H4 were depleted due to their condensation sink located deeper than 5 mbar outside the southern polar vortex. HCN, C4H2, and CH3C2H volume mixing ratio cross section contours showed steep slopes near the mid-latitudes or close to the equator, which can be explained by upwelling air in this region. Upwelling is also supported by the cross section of the C2H4 (the only molecule not condensing among those studied here) volume mixing ratio observed in the northern hemisphere. We derived the zonal wind velocity up to mesospheric levels from the retrieved thermal field. We show that zonal winds were faster and more confined around the south pole in 2015 (Ls = 67−72°) than later. In 2016, the polar zonal wind speed decreased while the fastest winds had migrated toward low-southern latitudes.

S Vinatier↗

Ground-based infrared spectroscopic measurements of atmospheric hydrogen cyanide

A number of lines of the nu-3 band of hydrogen cyanide have been detected in solar absorption spectra recorded near sunrise and sunset at Kitt Peak National Observatory (elevation 2095 m) with a 0.01/cm resolution Fourier transform spectrometer. Analysis of two of the strongest and best isolated lines has led to a value of 2.73 x 10 to the 15th molecules/sq cm for the vertical column abundance of HCN above Kitt Peak. The accuracy of this value is estimated as + or - 25%. This result, combined with the stratospheric concentration of HCN derived by Coffey, Mankin, and Cicerone (1981), yields 166 parts per trillion by volume for the average mixing ratio of HCN between 2 and 12 km. This is the first determination of the HCN concentration in the nonurban troposphere.

Rinsland, C. P.↗

Chemical effects of large impacts on the earth's primitive atmosphere

The production of HCN and H2CO by large impacts on the earth's primitive atmosphere is modelled using thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures, and initial compositions. For atmospheres with C/O of one or more, the results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10 to the -3rd to -5th in the impact region and global average ratios of 10 to the -5th to the -12th. The corresponding H2CO mixing ratios in the impact region are 10 to the -7th to -9th; nonglobal mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15 percent of the HCN produced can provide 3-14 x 10 to the 11th mol HCN per year.

Fegley, B., Jr.↗

Role of the methylene amidogen (H2CN) radical in the atmospheres of Titan and Jupiter

The methylene amidogen (H2CN) radical can be shown to be an important intermediate in models for the formation of HCN (via N + CH3) and the recombination of H to H2 (via H + HCN) on Titan as well as in models for the formation of HCN (via NH2 + C2H3) in the atmosphere of Jupiter. Experiments in our laboratory in a discharge flow system with mass spectrometric detection of both reactants and products have established that the major product channel (90 percent for the reaction N + CH3 is that leading to H2CN + H. The same result was obtained for N + CD3 yields D2CN + D. The rate constant for the reaction D + D2CN yields DCN + D2 was measured for the first time and k(298 K) greater than 7 x 10(exp -11) cu cm/s was found. The same result was obtained for the H atom reaction. This is the final step in the reaction sequence leading to HCN on both Titan and Jupiter and to formation of H2 from H on Titan. The first measurement of the ionization potentials for H2CN and D2CN was also made. From electron impact studies I.P. = (9.6 + or - 1.0) eV was obtained for both radicals. An upperlimit of I.P. less than 11.6 eV came from observations of the H2CN radical by photoionization mass spectrometry using an Ar resonance lamp (106.7 nm). Further photoionization experiments are planned using synchrotron radiation plus monochromator as a tunable vacuum UV light source.

Nesbitt, F. L.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

Atmospheric Pseudohalogen Chemistry

Hydrogen cyanide is not usually considered in atmospheric chemical models. The paper presents three reasons why hydrogen cyanide is likely to be significant for atmospheric chemistry. Firstly, HCN is a product and marker of biomass burning. Secondly, it is also likely that lightning is producing HCN, and as HCN is sparingly soluble it could be a useful long-lived "smoking gun" marker of lightning activity. Thirdly, the chemical decomposition of HCN leads to the production of small amounts of the cyanide (CN) and NCO radicals. The NCO radical can be photolyzed in the visible portion of the spectrum yielding nitrogen atoms (N). The production of nitrogen atoms is significant as it leads to the titration of total nitrogen from the atmosphere via N+N->N2, where N2 is molecular nitrogen.

Lary, David John↗

Trace Gas Measurements in Nascent, Aged and Cloud-processed Smoke from Africa Savanna Fires by Airborne Fourier Transform Infrared Spectroscopy (AFTIR)

We measured stable and reactive trace gases with an airborne Fourier transform infrared spectrometer (AFTIR) on the University of Washington Convair-580 research aircraft in August/September 2000 during the SAFARI 2000 dry season campaign in Southern Africa. The measurements included vertical profiles of C02, CO, H20, and CH4 up to 5.5 km on six occasions above instrumented ground sites and below the TERRA satellite and ER-2 high-flying research aircraft. We also measured the trace gas emissions from 10 African savanna fires. Five of these fires featured extensive ground-based fuel characterization, and two were in the humid savanna ecosystem that accounts for most African biomass burning. The major constituents we detected in nascent CH3OOH, HCHO, CH30H, HCN, NH3, HCOOH, and C2H2. These are the first quantitative measurements of the initial emissions of oxygenated volatile organic compounds (OVOC), NH3, and HCN from African savanna fires. On average, we measured 5.3 g/kg of OVOC and 3.6 g/kg of hydrocarbons (including CH4) in the initial emissions from the fires. Thus, the OVOC will have profound, largely unexplored effects on tropical tropospheric chemistry. The HCN emission factor was only weakly dependent on fire type; the average value (0.53 g/kg) is about 20 times that of a previous recommendation. HCN may be useful as a tracer for savanna fires. Delta O3/Delta CO and Delta CH3COO/Delta CO increased to as much as 9% in <1 h of photochemical processing downwind of fires. Direct measurements showed that cloud processing of smoke greatly reduced CH30H, NH3, CH3COOH, SO2, and NO2 levels, but significantly increased HCHO and NO.

Yokelson, Robert J.↗

Temporal and Spatial Aspects of Gas Release During the 2010 Apparition of Comet 103P/Hartley-2

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 .

Mumma, M. J.↗

Post-Perihelion Volatile Production and Release from Jupiter-Family Comet 45P/Honda-Mrkos-Pajdušáková

High-resolution infrared spectra of Jupiter-family comet 45P/Honda-Mrkos-Pajdušáková were obtained with NIRSPEC at the W. M. Keck Observatory on two post- perihelion dates (UT 2017 February 13 and 19), when the comet was at heliocentric distances of 1.01 and 1.10 AU, respectively. On UT February 13, H2O was measured simultaneously with six trace parent molecules: CH3OH, C2H6, HCN, NH3, C2H2, and H2CO. On UT February 19, CH4 and CO were also targeted in addition to the species measured on UT February 13. Abundances of CO, CH4, and C2H2 relative to H2O are consistent with values obtained from IRTF/iSHELL observations of 45P in early January 2017 just after perihelion when the heliocentric distance was 0.55–0.56 AU. Differences are seen in H2CO/H2O, C2H6/H2O, CH3OH/H2O, and HCN/H2O in February compared to January. Additionally, NH3 abundances appear highly variable during the February measurements, suggesting possible fluctuations of a factor of ten; however, there is significant uncertainty in quantifying NH3 owing to the marginal detections of only one or two lines on each of the two dates. Combining all infrared spectroscopic observations of 45P in January and February 2017, a post-perihelion relationship of Q(H2O) = (2.81 ± 0.25) × 10(exp 27) [R(sub h) (sup −3.83 ± 0.18)] molecules/s is derived. However, all measurements suggest significant variability in H O production on timescales of hours and days. Compared to other comets, volatile abundances relative to H2O in 45P are as follows: CO (depleted relative to all measured comets), CH3OH (enriched/all comets), CH4 and C2H6 (typical/all comets, enriched/Jupiter-family comets), C2H2 (depleted/all comets, typical/Jupiter-family comets), H2CO (January: typical, February depleted/all comets), HCN (January: severely depleted, February: typical/Jupiter-family comets). The small geocentric distances of the comet in February 2017 provide high spatial resolution in the coma of 45P (~12 and 19 km/pixel on February 13 and 19, respectively). Overall, the spatial distributions of volatiles and dust suggest a relatively symmetric and uniform coma during the UT February 13 and 19 observations, with small spatial differences noted between some volatile species. Measured C2H2 and HCN abundances are consistent with HCN as the primary parent of CN and C2H2 as a significant but not primary parent for C2, based on C2 and CN 2017 and previous apparitions. Extracted spectra show an increase in the dust-to-gas ratio in 45P from February 13 to 19 in agreement with contemporaneous narrowband optical measurements.

Russo, Neil Dello↗

Electronic transition CN laser

A 20 kW electric-discharge pumped CN laser oscillating on the A(2) Pi-X(2) Sigma molecular system is presented. Excitation is by a simple longitudinal discharge struck through HCN vapor. Twenty kW peak power is generated in a 150 nsec full-width half-maximum pulse. Two lasing bands were observed in the A-X system: the (0,1) and (0,2) bands near 1.42 and 2.0 microns respectively. Both P and Q branches are active in the two bands, with Q bands stronger. Peak laser energy is 3 mJ. Products of UV photolysis of HCN, electron impact excitation of HCN, and other possible excitation mechanisms and laser efficiency are discussed.

Quick, C. R., Jr.↗

Chemical evolution. XXIX - Pyrimidines from hydrogen cyanide

Compounds obtained by hydrolysis of HCN oligomers formed by allowing pH 9.2, 0.1 M cyanide to stand at room temperature for 4 to 12 months were analyzed. Hydrolysis of HCN oligomers yielded 4,5-dihydroxypyrimidine and 5-hydroxyuracil; orotic acid was detected after hydrolysis at pH 8.5. A unified pathway from diaminofumaronitrile to the pyrimidines observed is suggested. As purines, pyrimidines and amino acids are released by hydrolysis of HCN oligomers in either acidic or mildly basic aqueous solutions, they could have been formed on the primitive earth in spite of fluctuations in pH. 4,5-dihydroxypyrimidines appear to be likely candidates for incorporation into primitive nucleic acids, as they should undergo Watson-Crick hydrogen bonding with adenine.

Ferris, J. P.↗

Rates of fixation by lightning of carbon and nitrogen in possible primitive atmospheres

A thermochemical-hydrodynamic model of the production of trace species by electrical discharges has been used to estimate the rates of fixation of C and N by lightning in the primitive atmosphere. Calculations for various possible mixtures of CH4, CO2, CO, N2, H2, and H2O reveal that the prime species produced were probably HCN and NO and that the key parameter determining the rates of fixation was the ratio of C atoms to O atoms in the atmosphere. Atmospheres with C more abundant than O have large HCN fixation rates, in excess of 10 to the 17th molecules/J, but small NO yields. However, when O is more abundant than C, the NO fixation rate approaches 10 to the 17th molecules/J while the HCN yield is small. The implications for the evolution of life are discussed.

Chameides, W. L.↗

Formation and photochemistry of methylamine in Jupiter's atmosphere

In the upper troposphere and lower stratosphere of Jupiter, translationally hot H atoms are produced in the photolysis of ammonia, phospine, and acetylene which react with methane to form methyl radicals. The latter combine with NH2 to form methylamine. It is presently shown that the combined production of methylamine and subsequent photolysis to HCN is unlikely to account for the HCN observed near Jupiter's tropopause. The recommendation of NH2 and C2H3 radicals to yield C2H5N, followed by photolysis to HCN, is the preferred path. An upper limit column density on CH3PH2 is estimated to be about 10 to the 13th/sq cm, as compared to 10 to the 15th/sq cm for CH3NH2.

Kaye, J. A.↗