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At least 145 records · Page 8

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↗

Designed 2D protein crystals as dynamic molecular gatekeepers for a solid-state device

The sensitivity and responsiveness of living cells to environmental changes are enabled by dynamic protein structures, inspiring efforts to construct artificial supramolecular protein assemblies. However, despite their sophisticated structures, designed protein assemblies have yet to be incorporated into macroscale devices for real-life applications. We report a 2D crystalline protein assembly of C98/E57/E66 L-rhamnulose-1-phosphate aldolase ( CEE RhuA) that selectively blocks or passes molecular species when exposed to a chemical trigger. CEE RhuA crystals are engineered via cobalt(II) coordination bonds to undergo a coherent conformational change from a closed state (pore dimensions <1 nm) to an ajar state (pore dimensions ~4 nm) when exposed to an HCN(g) trigger. When layered onto a mesoporous silicon (pSi) photonic crystal optical sensor configured to detect HCN (g) , the 2D CEE RhuA crystal layer effectively blocks interferents that would otherwise result in a false positive signal. The 2D CEE RhuA crystal layer opens in selective response to low-ppm levels of HCN (g) , allowing analyte penetration into the pSi sensor layer for detection. These findings illustrate that designed protein assemblies can function as dynamic components of solid-state devices in non-aqueous environments.

36 MATERIALS SCIENCE↗

James Clerk Maxwell Telescope Spectral and Continuum Imaging of Hyperactive Comet 46P/Wirtanen

The Jupiter-family comet (JFC) 46P/Wirtanen passed the Earth at a distance of 0.077 au on 2018 December 16 UT, presenting a rare opportunity to study the chemical structure of its coma. With the James Clerk Maxwell Telescope we achieved a resolution of 800 km, which is smaller than the scale lengths of some distributed cometary molecules at the comet’s heliocentric distance of 1 au. Spectroscopic observations of the J = 4 - 3 transition of HCN showed generally uniform levels of outgassing activity during the observing period, 2018 December 14–20. Gas expansion velocities were ~0.6 km s{sup -1}, and the derived average HCN production rate was 7.4 × 10{sup 24} mol s{sup -1}. HCN and CH{sub 3}OH emissions were detected at least 30" (1600 km) from the nucleus, and the abundances of these species were typical for a JFC. The radial distribution of CH{sub 3}OH is consistent with an extended source of sublimation such as a population of icy grains—cometary halo ice primaries, or CHIPs—as has been invoked previously to explain hyperactivity in comets. The abundance of H{sub 2}CO is normal if it is a daughter species. HNC and CO were not detected, but a sensitive nondetection of CS implies an unusually low CS:H{sub 2}O ratio of <0.02%. The peak brightness of the 850 μm continuum emissions from icy coma dust particles of size ~1 mm fell from (52 ± 6) to (40 ± 3) mJy beam{sup -1} through the week, while the size of the dust coma remained essentially constant, with dust extending to ~1000 km from the nucleus. The total mass of those particles was ~2 × 10{sup 8} kg.

79 ASTRONOMY AND ASTROPHYSICS↗

A Near-infrared Chemical Inventory of the Atmosphere of 55 Cancri e

We present high-resolution near-infrared spectra taken during eight transits of 55 Cancri e, a nearby low-density super-Earth with a short orbital period (<18 hr). While this exoplanet’s bulk density indicates a possible atmosphere, one has not been detected definitively. Our analysis relies on the Doppler cross-correlation technique, which takes advantage of the high spectral resolution and broad wavelength coverage of our data, to search for the thousands of absorption features from hydrogen-, carbon-, and nitrogen-rich molecular species in the planetary atmosphere. Although we are unable to detect an atmosphere around 55 Cancri e, we do place strong constraints on the levels of HCN, NH{sub 3}, and C{sub 2}H{sub 2} that may be present. In particular, at a mean molecular weight of 5 amu, we can rule out the presence of HCN in the atmosphere down to a volume mixing ratio (VMR) of 0.02%, NH{sub 3} down to a VMR of 0.08%, and C{sub 2}H{sub 2} down to a VMR of 1.0%. If the mean molecular weight is relaxed to 2 amu, we can rule out the presence of HCN, NH{sub 3}, and C{sub 2}H{sub 2} down to VMRs of 0.001%, 0.0025%, and 0.08%, respectively. Our results reduce the parameter space of possible atmospheres consistent with the analysis of Hubble Space Telescope/WFC3 observations by Tsiaras et al. and indicate that if 55 Cancri e harbors an atmosphere, it must have a high mean molecular weight or clouds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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.↗

Prebiotic synthesis in atmospheres containing CH4, CO, and CO2. I - Amino acids

The prebiotic synthesis of amino acids, HCN, H2CO, and NH3 using a spark discharge on various simulated primitive earth atmospheres at 25 C is investigated. Various mixtures of CH4, CO, CO2, N2, NH3, H2O, and H2 were utilized in different experiments. The yields of amino acids (1.2-4.7 percent based on the carbon) are found to be approximately independent of the H2/CH4 ratio and the presence of NH3, and a wide variety of amino acids are obtained. Glycine is found to be almost the only amino acid produced from CO and CO2 model atmospheres, with the maximum yield being about the same for the three carbon sources at high H2/carbon ratios,whereas CH4 is superior at low H2/carbon ratios. In addition, it is found that the directly synthesized NH3 together with the NH3 obtained from the hydrolysis of HCN, nitriles, and urea could have been a major source of ammonia in the atmosphere and oceans of the primitive earth. It is determined that prebiotic syntheses from HCN and H2CO to give products such as purines and sugars and some amino acids could have occurred in primitive atmospheres containing CO and CO2 provided the H2/CO and H2/CO2 ratios were greater than about 1.0.

Schlesinger, G.↗

Studies of radiative transfer in planetary atmospheres

A set of high signal-to-noise spectra of the 18 cm OH emission from the comet P/Halley was obtained. During the course of the Halley OH campaign, high signal-to-noise spectra were also obtained on the comets P/Giacobini-Zinner, C/Thiele, and C/Hartley-Good. The HCN observations of Comet Halley were performed during a total of 56 individual observing sessions between 18 November 1985 and 11 May 1986. These observations represent the largest monitoring program of HCN emission from any comet, and moreover, represent the first time that a cometary parent molecule was so extensively observed. In addition to offering a direct means to monitor the production of a parent molecule from the nucleus, these data also provide fundamental information about the kinematics of parent molecules in the coma. Finally, in addition to monitoring HCN from the comet, attempts were also made to detect other molecues via millimeter-wave spectroscopy. Future plans are descussed.

Irvine, W. M.↗

HCNH(+) - A new interstellar molecular ion

The first interstellar detection of HCNH(+) is reported. The J = 1-0, 2-1, and 3-2 rotational transitions of this molecule at 74, 148, and 222 GHz have been observed toward Sgr B2. Using a large velocity gradient model calculation, the column density of HCNH(+) is found to be about 4 x 10 to the 14th/sq cm, about one order of magnitude less than that estimated for HCO(+) and HCN in this source. Such a column density implies a fractional abundance of at least one to several orders of magnitude larger than predicted by numerous ion-molecule models. Coupled with a relatively low abundance of HCN and a small HNC/HCN ratio, this suggests that HCNH(+) is not channeled into HCN or HNC as rapidly as thought.

Ziurys, L. M.↗