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NASA NTRS1981

The detection of HCN on Jupiter

The detection of HCN on Jupiter is reported. Three R-branch lines of the nu-2 fundamental of HCN near 13.5 microns were observed in absorption, from which the HCN column density is inferred to be 0.005 cm-am with an uncertainty of a factor of two. If emission from the stratosphere exists, then the derived column density is only a lower limit. It is suggested that the Jovian HCN most likely originates from the photolysis of CH4 and NH3 in the lower stratosphere and upper troposphere. In addition, an upper limit of 0.025 cm-am was established for the column density of HCN on Saturn.

Tokunaga, A. T.↗
NASA NTRS1990

Simultaneous imaging of optical CN lines and radio HCN lines in comet Austin

The parent molecule of cometary CN has been the subject of speculation for a long time. When HCN was detected at 3.4 mm in Comet Kohoutek, the problem seemed to be resolved, but much more detailed work on Comet Halley raised the quantitative question of whether HCN could be the only parent. Therefore, comparative CN/HCN studies are vital for understanding the origin of cometary CN. The striking observation of CN jets in Comet Halley raised another very interesting question about the origin of CN. Traditional theory permits only dust features to remain well defined far from the nucleus. The CN jets were interpreted as arising from submicron sized dust particles, perhaps CHON particles. An estimated 10 to 50 percent of the CN in the comet was in the jets in the Halley observations. Several hypotheses can be made: (1) some of the CN originates from the dust and has nothing to do with HCN; or, (2) at least some of the HCN is also produced from the dust in the coma rather than directly from the nucleus. (In the second hypothesis, whether CHN is or is not the parent of the CN associated with the dust would need to be established.) The extended scalelengths found for CO by Eberhardt et. al. (1987) and for H2CO by Snyder et. al. (1989) also support ideas like hypothesis (2). A third hypothesis should be mentioned; contrary to the usual theory, the gas flow does not become isotropic (Combi 1987). For all of the reasons mentioned, it is essential to make a detailed comparison of the spatial distributions of CN and HCN. Furthermore, because of the variability of cometary emissions, it is necessary to make measurements simultaneously.

Palmer, Patrick↗
NASA NTRS2002

Synthesis of HCN and HNC in Ion-Irradiated N2-Rich Ices

Near-IR observations reveal that N2-rich ice containing small amounts of CH4, and CO, is abundant on the surfaces of Triton, a moon of Neptune, and Pluto. N2-rich ices may also exist, in interstellar environments. To investigate the radiation chemistry of such ices we performed a systematic IR study of ion-irradiated Nz-rich mixtures containing CH4 and CO. Irradiation of N2 + CH4 mixtures at 12 K, showed that HCN, HNC, diazomethane, and NH3 were produced. We also found that UV photolysis of these ices produced detectable HCN and HNC. Intrinsic band strengths, A(HCN) and A(HNC), were measured and used to calculate yields of HCN and HNC. Similar results were obtained on irradiation of N2 + CH4 + CO ices at 12 K, with the main difference being the formation of HNCO. In all cases we observed changes on warming. For example, when the temperature of irradiated Nz + CH4 + CO was raised from 12 to 30 K, HCN, HNC, and HNCO reacted with NH3, and OCN-, CN-, N3-, and NH4+ were produced. These ions, appearing at 30 K, are expected to form and survive on the surfaces of Triton, Pluto, and interstellar grains. Our results have astrobiological implications since some of these radiation products are involved in the syntheses of biomolecules such as amino acids and peptides.

Moore, M. H.↗
NASA NTRS1985

Spectroscopic measurements of atmospheric HCN at northern and southern latitudes

A number of lines belonging to the nu(3) fundamental vibration-rotation band of hydrogen cyanide (HCN) have been identified in atmospheric infrared absorption spectra obtained on high-altitude balloon flights at 32 deg N in 1976 and at 30 deg S in 1977. Quantitative analysis of these spectral features has resulted in the first determination of atmospheric HCN concentrations in the Southern Hemisphere, as well as an independent estimate of stratospheric HCN abundance in the Northern Hemisphere. Within the uncertainties of the present and previous measurements, the Northern Hemisphere result is consistent with those of other investigators, and Southern Hemisphere HCN concentrations appear to be similar to those in the Northern Hemisphere.

Smith, M. A. H.↗
NASA NTRS1986

Detection of interstellar vibrationally excited HCN

The J = 3 - 2 rotational transitions of the l-doubled bending mode of HCN have been detected toward Orion-KL and IRC + 10216, representing the first interstellar medium observations of vibrationally excited HCN. The overall column density in the (0, 1, 0) mode exclusively sampling the hot core is 1.7 x 10 to the 16th/sq cm, and may be understood in terms of the doughnut model for Orion. The ground state HCN column density implied by the excited state observations is at least one order of magnitude greater than the column densities derived for HCN in its spike and plateau/doughnut components. The spectral profiles obtained have been modeled to yield abundances and excitation conditions throughout the expanding envelope.

Ziurys, L. M.↗
NASA NTRS1986

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Zahnle, K. J.↗
NASA NTRS1986

HCN production from comet Halley

The HCN J = 1-0 rotational transition at 3.4 mm wavelength has been detected and has been monitored in comet P/Halley during a total of 56 individual observing sessions between November 18, 1985 and May 11, 1986. The HCN spectra show significant daily variations in total intensity, but the average HCN production rate is well correlated with the visual magnitude of the comet over the range of heliocentric distance observed (between 0.59 and 1.8). Observations of the ratios of the F = 2-1 and F = 1-1 hyperfine components also exhibit significant daily variations but are, in the mean, consistent with the 5:3 ratio expected from the statistical weights of the hyperfine levels. The outflow velocity of the coma, deduced from the HCN linewidths, is 0.87 + or - 0.12 km/s, which is consistent with recent theoretical estimates as well as the measurements of the Giotto spacecraft.

Schloerb, F. Peter↗
NASA NTRS1987

Energy yields for hydrogen cyanide and formaldehyde syntheses - The HCN and amino acid concentrations in the primitive ocean

Simulated prebiotic atmospheres containing either CH4, CO, or CO2, in addition to N2, H2O, and variable amounts of H2, were subjected to the spark from a high-frequency Tesla coil, and the energy yields for the syntheses of HCN and H2CO were estimated from periodic (every two days) measurements of the compound concentrations. The mixtures with CH4 were found to yield the highest amounts of HCN, whereas the CO mixtures produced the highest yields of H2CO. These results model atmospheric corona discharges. From the yearly energy yields calculated and the corona discharge available on the earth, the yearly production rate of HCN was estimated; using data on the HCN production rates and the experimental rates of decomposition of amino acids through the submarine vents, the steady state amino acid production rate in the primitive ocean was calculated to be about 10 nmoles/sq cm per year.

Stribling, Roscoe↗
NASA NTRS1993

Molecular clouds in the centers of galaxies: Constraints from HCN and CO-13 line emission

We have searched for HCN J=1-0 line emission in the centers of 12 galaxies and have detected it in 10 of them. We have obtained complementary data on J=1-0 and 2-1 transitions of CO-12 and CO-13 in these systems. The ratio of integrated intensities, I(CO 1-0)/I(HCN 1-0) = 25 +/- 11 for this sample. We find that HCN emission of this strength can be produced under conditions of subthermal excitation. In combination with the line ratios in CO and CO-13, HCN puts constraints on the mean conditions of molecular clouds and on the mix of cloud types within the projected beam.

Aalto, S.↗
NASA NTRS1994

A search for SiO, OH, CO and HCN radio emission from silicate-carbon stars

We report upper limits for radio emission of SiO at 86 and 43 GHz, of OH at 1612 and 1665/1667 MHz, of CO at 115 GHz and HCN at 88.6 GHz in the silicate-carbon stars. These upper limits of SiO imply that oxygen-rich material has not been detected within 2R(sub star) of a central star even though the detected emission from silicate dust grains, H2O and OH maser establishes the presence of oxygen-rich material from about tens to thousands of AU of a central star. The upper limit of the SiO abundance is consistent with that found in oxygen-rich envelopes. Upper limits of the mass loss rate (based on the CO data) are estimated to be between 10(exp -6) to 10(exp -7) solar mass/yr assuming a distance of 1.5 kpc for these stars. The absence of HCN microwave emission implies that no carbon-rich material can be detected at large distances (thousands of AU) from a central star. The lack of detections of SiO, CO, and HCN emission is most likely due to the large distances of these stars. A number of C stars were detected in CO and HCN, but only the M supergiant VX Sgr was detected in CO.

Little-Marenin, I. R.↗
NASA NTRS1995

HCN and HCO(+) images of the photodissociation region in the Orion Bar

We present preliminary millimeter-wavelength images of the photodissociation region (PDR) in the Orion Bar, observed with the Berkeley- Illinois-Maryland array (BIMA). These new BIMA observations have attained 5 arc sec resolution in the J=l-O emission lines of HCO+ (formyl ion) and HCN (hydrogen cyanide). The results are compared with previous observations of the J=1-0 transition lines of (13)CO. We find that the HCO+ and HCN have different spatial distributions. HCN appears to lie primarily inside dense clumps of gas, which are defined by areas of intense (13)CO emission. However, the HCO+ emission appears to be only loosely associated with the surfaces of the gas clumps. We suggest that HCO+ abundance is enhanced by the presence of vibrationally excited H2 on the surfaces of dense clumps, and that the HCN abundance is attenuated by photo destruction outside the cores of dense clumps of gas.

Youngowl, Rolaine C.↗
NASA NTRS1997

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Hoobler, Ray J.↗
NASA NTRS1999

Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Tropical Fires of 1997-1998

High spectral resolution (0.003 per cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5N, 155.6W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4-16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first 2 years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4-16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32'N and 45'S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4-16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during the strong El Nino warm phase of 1997- 1998 are the likely source of the elevated emission products.

Rinsland, C. P.↗
NASA NTRS1999

Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Fires of 1997-1998

High spectral resolution (0.003/ cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5 deg N, 155.6 deg W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4 - 16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first two years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4 - 16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32 deg N and 45 deg S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4 - 16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during 3 the strong El Nino warm phase of 1997-1998 are the likely source of the elevated emission products.

Rinsland, C. P.↗
NASA NTRS1994

Optical properties of poly-HCN and their astronomical applications

Matthews (1992) has proposed that HCN "polymer" is ubiquitous in the solar system. We apply vacuum deposition and spectroscopic techniques previously used on synthetic organic heteropolymers (tholins), kerogens, and meteoritic organic residues to the measurement of the optical constants of poly-HCN in the wavelength range 0.05-40 micrometers. These measurements allow quantitative comparison with spectrophotometry of organic-rich bodies in the outer solar system. In a specific test of Matthews' hypothesis, poly-HCN fails to match the optical constants of the haze of the Saturnian moon, Titan, in the visible and near-infrared derived from astronomical observations and standard models of the Titan atmosphere. In contrast, a tholin produced from a simulated Titan atmosphere matches within the probable errors. Poly-HCN is much more N-rich than Titan tholin.

Optics↗
NASA NTRS2016

Alma Observations of HCN and its Isotopologues on Titan

We present sub-millimeter spectra of HCN isotopologues on Titan, derived from publicly available ALMA flux calibration observations of Titan taken in early 2014. We report the detection of a new HCN isotopologue on Titan, H13C15N, and confirm an earlier report of detection of DCN. We model high signal-to-noise observations of HCN, H13CN, HC15N, DCN, and H13C15N to derive abundances and infer the following isotopic ratios: 12C/13C = 89.8 +/- 2.8, 14N/15N = 72.3 +/- 2.2, D/H = (2.5 +/- 0.2) × 10−4, and HCN/H13C15N = 5800 +/- 270 (1sigma errors). The carbon and nitrogen ratios are consistent with and improve on the precision of previous results, confirming a factor of approximately 2.3 elevation in 14N/15N in HCN compared to N2 and a lack of fractionation in 12C/13C from the protosolar value. This is the first published measurement of D/H in a nitrile species on Titan, and we find evidence for a factor of approximately 2 deuterium enrichment in hydrogen cyanide compared to methane. The isotopic ratios we derive may be used as constraints for future models to better understand the fractionation processes occurring in Titan's atmosphere.

Molter, Edward M.↗
NASA NTRS1978

An upper limit to the interstellar abundance of the HCN dimer

An unsuccessful search is described for the J = 7-6 transition of HCN ... HCN in several interstellar clouds known to be rich in HCN. An upper limit to the abundance of the dimer relative to the monomer is typically 1 percent. It is suggested that this implies a low abundance for similar weakly bound species.

Storey, J. W. V.↗
NASA NTRS1978

HCN - A plausible source of purines, pyrimidines and amino acids on the primitive earth

Dilute (0.1 M) solutions of HCN condense to oligomers at pH 9.2, and hydrolysis of these oligomers yields 4,5-dihydroxypyrimidine, orotic acid, 5-hydroxyuracil, adenine, 4-aminoimidazole-5-carboxamide, and amino acids. It is suggested that the three main classes of nitrogen-containing biomolecules - purines, pyrimidines, and amino acids may have originated from HCN on the primitive earth. It is also suggested that the presence of orotic acid and 4-aminoimidazole-5-carboxamide might indicate that contemporary biosynthetic pathways for nucleotides evolved from the compounds released on hydrolysis of HCN oligomers.

Ferris, J.-P.↗