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Chemistry and spectroscopy of the Jovian atmosphere

A comprehensive review is given of the chemistry and spectroscopic studies of the Jovian atmosphere. Thermochemical equilibrium models for determining atmospheric composition are considered along with possible disequilibrating processes, and studies of the photochemistry of H2, CH4, NH3, H2S, and PH3 using the modeling methods are summarized. It is shown that photodissociation and advection are the major disequilibrating processes in Jupiter's atmosphere, that lightning and charged-particle bombardment are relatively minor factors in the planet's bulk chemistry, and that the existence of living organisms on the planet is highly improbable. Spectroscopic investigations of Jupiter are discussed, emphasizing recent observations of absorption bands due to CH4, NH3, H2, He, and D. Spectroscopic abundance determinations are examined for H2, HD, CH4, CH3D, NH3, C2H6, C2H2, and PH3. Upper limits are given for the abundances of several unobserved gases in the visible atmosphere, including H2S, HCl, SiH4, benzene, purines, pyrimidines, and their derivatives.

Prinn, R. G.↗

Crossed beam studies of ion-molecule reactions in methane and ammonia

A crossed-beam apparatus is used to measure the product ion velocity and angular distributions for the following ion-molecule reactions in the relative energy range from 2 to 9 eV: CH4(+) + NH3 yields NH4(+) + CH3; CH4(+) + NH3 yields CNH5(+) + H2; NH2(+) + CH4 yields CNH4(+) + H2 (or 2H); and CH3(+) + NH3 yields CNH4(+) + H2 (or 2H). These reactions are also studied by means of deuterium labeling as a further probe of the detailed reaction dynamics. Probability contour plots for the four reactions are constructed in Cartesian velocity space, and product peaks in the plots are discussed. Relative cross sections and Q values are computed for two of the reactions as well as for the corresponding deuterium-labelled reactions. The results show that the present ion-neutral condensation reactions are highly exothermic with a deep well for the internal complex, that little hydrogen scrambling occurs, and that the energy of the reactions is released mainly as internal energy, even to the extent of producing two hydrogen atoms in some cases rather than one hydrogen atom or molecule.

Smith, G. P. K.↗

A saturation model of the atmosphere of Uranus

A model of the atmospheric structure of Uranus is presented which differs from previous types of models in two important respects: (1) the CH4/H2 ratio is sufficiently large that CH4 is saturated to large depths in the Uranian atmosphere and (2) the internal energy flux is small compared with that due to solar heating. Because of the small internal flux, the thermal flux decreases rapidly with depth and the atmosphere is radiative to large optical depths. A CH4 droplet cloud forms where the atmosphere finally becomes convective due to the internal flux. The model is shown to be in reasonable agreement with published observations of the H2 quadrupole 3-0 and 4-0 bands, the visible (4000-6000 A) CH4 bands, and the infrared emission spectrum.

Danielson, R. E.↗

Organic chemistry on Titan

Observations of nonequilibrium phenomena on the Saturn satellite Titan indicate the occurrence of organic chemical evolution. Greenhouse and thermal inversion models of Titan's atmosphere provide environmental constraints within which various pathways for organic chemical synthesis are assessed. Experimental results and theoretical modeling studies suggest that the organic chemistry of the satellite may be dominated by two atmospheric processes: energetic-particle bombardment and photochemistry. Reactions initiated in various levels of the atmosphere by cosmic ray, Saturn wind, and solar wind particle bombardment of a CH4 - N2 atmospheric mixture can account for the C2-hydrocarbons, the UV-visible-absorbing stratospheric haze, and the reddish color of the satellite. Photochemical reactions of CH4 can also account for the presence of C2-hydrocarbons. In the lower Titan atmosphere, photochemical processes will be important if surface temperatures are sufficiently high for gaseous NH3 to exist. Hot H-atom reactions initiated by photo-dissociation of NH3 can couple the chemical reactions of NH3 and CH4 and produce organic matter.

Chang, S.↗

16-30 micron spectroscopy of Titan

Titan has been observed from 16 to 30 micron with a resolution of 1 micron. Earlier broad-band data are consistent with the new measurements, which show that the disk integrated flux is nearly constant over the observed range of wavelengths. Limits on the CH4, H2, and N2 column densities and pressures at the bottom of the upper layer are derived. These indicate that if the atmosphere gas is CH4, an H2-CH4 mix, or N2, the inversion layer must be at pressures less than 30 millibars.

Mccarthy, J. F.↗

Comments on Pluto's atmosphere

A pure CH4 atmosphere would rapidly escape from Pluto. For such an atmosphere, even CH4 frosts on Pluto's surface would completely sublimate on a time scale short compared to Pluto's life. Observations of CH4 therefore imply that its atmosphere must also contain another gas in significant quantity.

Trafton, L.↗

Kinetic inhibition of CO and N2 reduction in circumplanetary nebulae - Implications for satellite composition

In contrast to the solar nebula, the conversion of CO to CH4 and of N2 to NH3 in the circumplanetary nebulae of the Jovian planets is fast enough relative to radial mixing and nebula cooling rates that CO and N2 are minor constituents in the circumplanetary nebulae. Thus, although the Jovian planets may have accreted carbon and nitrogen from the solar nebula mainly in the form of CO and N2, these species were then reprocessed within the circumplanetary nebulae to form mainly CH4 and NH3. Satellites of the Jovian planets which accreted in sufficiently cool parts of their circumplanetary nebula are therefore predicted to retain large amounts of NH3 and CH4 in the form of clathrate hydrates and also very small but chemically important amounts of HCN.

Prinn, R. G.↗

Methane and nonmethane hydrocarbon concentrations in the North and South Atlantic marine boundary layer

Methane and nonmethane hydrocarbon (NMHC) data were collected in the Atlantic marine boundary layer from 40 N to 32 S latitude during October and November 1980. Average volume mixing ratios for CH4 of 1.69 + or - 0.02 ppmv were obtained north of the intertropical convergence zone (ITCZ) and 1.60 + or - 0.02 ppmv south of the ITCZ. The hemispheric CH4 gradient was very sharp, decreasing rapidly between 14 N and 10 N latitude. Gaseous NMHC concentrations (based on response as CH4) were measured simultaneously and found to lie consistently within the standard error for the individual measurements + or - 0.02 ppmv) after correction for water vapor interference. The correction for water vapor response was large, frequently as much as 80% of the raw NMHC signal. Application of the student's t distribution test to the NMHC data set established that the mean northern and southern hemispheric NMHC mixing ratios measured, 0.016 and 0.010 ppmv, respectively, were statistically different at the 95% confidence level. These results indicate volatile NMHC mixing ratios average less than 0.02 ppmv over the Atlantic and represent the first set of semicontinuous NMHC measurements spanning the North and South Atlantic marine boundary layer.

Cofer, W. R., III↗

The atmosphere of Titan - An analysis of the Voyager 1 radio occultation measurements

The equatorial atmosphere of Titan was probed by means of two coherently related radio signals transmitted from Voyager 1 at 13.0 and 3.6 cm wavelengths during the November 12, 1980 occultation of the spacecraft by the Saturn satellite. An analysis of the differential dispersive frequency measurements did not reveal any ionization layers in the upper atmosphere of Titan. The gas refractivity data, which extend from the surface to about 200 km altitude, were interpreted in two different ways. In the first, it is assumed that N2 makes up virtually all of the atmosphere, with small amounts of CH4 and other hydrocarbons present. In the second interpretation of the refractivity data, it is assumed that the 3.5 km altitude level corresponds to the bottom of a CH4 cloud layer and that N2 and CH4 were perfectly mixed below this level.

Lindal, G. F.↗

Methane flux across the air-water interface - Air velocity effects

Methane loss to the atmosphere from flooded wetlands is influenced by the degree of supersaturation and wind stress at the water surface. Measurements in freshwater ponds in the St. Marks Wildlife Refuge, Florida, demonstrated that for the combined variability of CH4 concentrations in surface water and air velocity over the water surface, CH4 flux varied from 0.01 to 1.22 g/sq m/day. The liquid exchange coefficient for a two-layer model of the gas-liquid interface was calculated as 1.7 cm/h for CH4 at air velocity of zero and as 1.1 + 1.2 v to the 1.96th power cm/h for air velocities from 1.4 to 3.5 m/s and water temperatures of 20 C.

Sebacher, D. I.↗

Longitudinal variability of methane and ammonia bands on Jupiter. II - Temporal variations

A set of spectra has been obtained of the Jovian equatorial zone central meridian 6190 A CH4 and 6450 A NH3 bands on the nights of February 26, 27, and 28, 1980, a year after the data reported by Cochran and Cochran (1980), in order to check the previous results and search for possible temporal variations. The new data confirm the results of the previous study. A correlation of the NH3 and CH4 equivalent widths, as well as a lack of any strong correlation of red continuum reflectivity with equivalent width, are found. Longitude regions of larger or smaller than average equivalent width still seem to exist a year later, with some slight drift in longitude. An increase in the average CH4 and NH3 equivalent width over the entire planet was detected during the one year interval. This is easily understood as the result of a global decrease in the mean altitude of the NH3 cloud.

Cochran, W. D.↗

Photochemistry of methane in the earth's early atmosphere

The photochemical behavior of methane in the early terrestrial atmosphere is investigated with a detailed model in order to determine how much CH4 might have been present and what types of higher hydroocarbons could have been formed. It is found that any primordial methane accumulated during the course of earth accretion would have been dissipated by photochemical reactions in the atmosphere in a geologically short period of time after the segregation of the core. Abiotic sources of methane are not likely to have been large enough to sustain CH4 mixing ratios as high as 10 to the -6th, the threshold for a possible methane greenhouse, with a CO-rich atmosphere being a possible exception. After the origin of life an increasing biogenic source of methane may have driven CH4 mixing ratios well above 10 to the 6th. The rise of atmospheric oxygen in the early Proterozoic may have led to a more rapid photochemical destruction of methane, lowering the mixing ratio to its present value.

Kasting, J. F.↗

High-resolution spectra of isotopic methanes near 1645 nm

It is demonstrated that the coincidence between Er:YAG laser emission and CH4 absorption is associated with the R(8) multiplet of C-13H4 instead of the R(6) of C-12H4. The Er:YAG emission was characterized as a laser emission at 6079.4/cm with a bandwidh of 2.2/cm and overlapping CH4 emission at 6078.7/cm. The R(6) component of C-12H4 closest to 6078.7/cm is calculated to be 6077.06/cm, corresponding to an absorption coefficient (AC) of 1.12/cm per atm. The F2-prime component of R(8) of C-13H4 has an AC of 0.308/cm per atm, which corresponds well with a range of 1.2-30.30/cm per atm based on a partial pressure of 1.6/89 ppm. The Er:YAG laser is a candidate for use in spectroscopic studies of CH4 atmospheric pollutants, natural gas movement and storage and gas accumulation in coal mines.

Fox, K.↗

Magmas as Selective Filters of Volatiles Between Planetary Mantles and Surfaces

The composition of early planetary atmospheres and biospheres which is a knowledge of the relationship between mantle volatiles and volcanic gases was analyzed. In the case of Earth it appears that volcanic rocks and gases are relatively oxidized compared to the upper mantle. In the case of the C-O-H volatiles, (H2O, CO2, CO, CH4, H2) the volcanic gases are enriched in H2O and CO2 while the volatiles in the mantle may be dominated by H2O, H2 and possibly CH4. An experimental technique was perfected for phase equilibrium studies in the 5-30 kbar range which allows accurate control of volatile species activities in the fluid phase. The system was used to measure the relative solubilities of H2O, CO2, CO, CH4 and H2 in magmas at 10 kbar pressure. It is found that mantle magmas will selectively screen volatiles from planetary surfaces, forcing volcanic gases towards the neutral QFM oxidation state where H2O is the dominant species.

Holloway, J. R.↗

Titan - Far-infrared and microwave remote sensing of methane clouds and organic haze

Titan's surface and plausible atmospheric thermal opacity sources, which include gaseous N2, CH4, and H2, together with CH4 clouds and organic haze, are sufficient to match available earth-based and Voyager observations of Titan's thermal emission spectrum. Dominant thermal emission sources are the surface, at greater than 1 cm wavelengths, atmospheric N2 for the 1-200 micron range, condensed and gaseous CH4 for 200-20 microns, and molecular bands and organic haze at less than 20 microns.

Thompson, W. R.↗

Methane concentrations and source strengths in urban locations

The results of a six year measurement of trace gases in 18 different urban and remote areas throughout the Northern and Southern Hemispheres are reported. It is found that the measurements are consistent with a yearly atmospheric release of 30 to 60 megatons of CH4 in urban environments. Concentrations of CCl3F, CCl2F2, and CH3CCl3 were also found to be higher in the same urban samples than in corresponding samples from remote areas. The 'urban excess' (urban concentration minus remote concentration) was generally 1000 to 2000 times larger on a molar basis for CH4 than for CCl3F. The fraction of world-wide methane release occurring in the urban environment is estimated from the concentration ratios for CH4 vs CCl3F. It is shown that about 8 to 15 percent of atmospheric methane release occurs in urban areas.

Blake, D. R.↗

Measurements of concentrations of chlorofluoromethanes (CFMs) carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems

Measurements of concentrations of chlorofluoromethanes (CFMs), carbon dioxide and carbon isotope ratio in stratospheric and tropospheric air by grab-sampling systems are reported. The balloon-borne grab-sampling system has been launched from Sanriku Balloon Center three times since 1981. It consists of: (1) six sampling cylinders, (2) eight motor driven values, (3) control and monitor circuits, and (4) pressurized housing. Particular consideration is paid to the problem of contamination. Strict requirements are placed on the choice of materials and components, construction methods, cleaning techniques, vacuum integrity, and sampling procedures. An aluminum pressurized housing and a 4-m long inlet line are employed to prevent the sampling air from contamination by outgassing of sampling and control devices. The sampling is performed during the descent of the system. Vertical profiles of mixing ratios of CF2Cl2, CFCl3 and CH4 are given. Mixing ratios of CF2Cl2 and CFCl3 in the stratosphere do not show the discernible effect of the increase of those in the ground level background, and decrease with altitude. Decreasing rate of CFCl3 is larger than that of CF2Cl2. CH4 mixing ratio, on the other hand, shows diffusive equilibrium, as the photodissociation cross section of CH4 is small and concentrations of OH radical and 0(sup I D) are low.

Itoh, T.↗

Titan's latitudinal temperature distribution and seasonal cycle

Voyager IRIS brightness temperature measurements of Titan at a wavelength of 530/cm are crudely indicative of ground or lower tropospheric temperatures and indicate 93 K for the equator and 91 K for both northern and southern high latitudes. The symmetry between north and south is unexpected for the time of Voyager encounter (Northern Titan spring). It is shown that this near-symmetry can arise naturally in a model where the poles are 'pinned' year-round at the dew point of CH4-N2 lakes or, more probably, a CH4-N2 rich surface layer on a deep ethane-rich ocean. For a polar temperature of 91 K, the model implies that the atmosphere contains somewhat less than 8 percent mole fraction of CH4.

Stevenson, D. J.↗