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At least 433 records · Page 24

Reservoirs of atmospheric chlorine - Prospects for HOCl revisited

Possible effects of HOCl aeronomy in the terrestrial stratosphere are reexamined. Chemical kinetics data for HOCl are analyzed which are required in aeronomical studies, and the possible role of HOCl as a reservoir of atmospheric chlorine is evaluated. Chemical production and loss of HOCl in the stratosphere is considered, along with photolysis of HOCl and prospects for HOCl as an inert chlorine reservoir. It is shown that a recent theoretical calculation of the HOCl photodissociation cross section suggests this species as a possible significant reservoir of atmospheric chlorine, but that the theoretical calculations are in sharp disagreement with some experimental measurements. Laboratory and atmospheric experiments to clarify the uncertainties of HOCl aeronomy are proposed.

Prasad, S. S.↗

Lyman-alpha and Balmer-series fluorescence from hydrogen photofragments of H2O vapor

Production cross sections associated with the atomic hydrogen Lyman-alpha and Balmer-series (3-9 to 2) fluorescence observed in H2O photodissociation are measured, and maximum fluorescence production cross sections for the two series are reported. Repulsive potential energy curves corresponding to the respective pseudodiatomic OH-H(n) molecule are constructed according to the Franck-Condon principle, and the efficiencies for converting H(2S) to H(2P) by H2 collisions and by H2O collisions are estimated. The data are considered with reference to cometary photochemistry.

Wu, C. Y. R.↗

Atomic to molecular hydrogen transition in interstellar clouds

The photodestruction of molecular hydrogen is reexamined in the context of recent observational data. Improvements in the theory of radiation transfer are made by using a more accurate self-shielding integral, treating anisotropic scattering by dust grains, and including photodissociation from excited rotational states. The total column density of hydrogen required to obtain 10% conversion decreases with a parameter, epsilon, the ratio of the formation rate to the destruction rate, as epsilon to the -m power, with m in the range 1.4-1.6. Satisfactory agreement with the data for thicker diffuse clouds is obtained for epsilon of about 0.00006.

Federman, S. R.↗

The reactions of CCl2FO2 with NO and NO2 and the thermal decomposition of CCl2FO2NO2

CCl2FO2 radicals are produced in the stratosphere from the oxidation of CCl2F radicals produced from the photodissociation of CCl3F. The reactions of CCl2FO2 with NO and NO2 were studied by steady state photolysis at 1 atm and 286-305 K. The reactions were CCl2FO2 + NO yields CCl2FO + NO2 and CCl2FO2 + NO2 (+M) yields CCl2FO2NO2 (+M) with k3/k4 = 0.58 plus or minus 0.10 over this temperature range.

Simonaitis, R.↗

A model of carbon production in a cometary coma

A model of the cometary ionosphere is developed in order to account for the large population of metastable C(D-1) atoms detected via the ultraviolet spectrum of Comet West (1976 VI). Dissociative recombination of CO(plus) ions and electrons is shown to be the dominant source of carbon atoms rather than photodissociation of CO so that the derived carbon production rate is only a lower limit to the evaporation rate of the carbon bearing mother molecule.

Feldman, P. D.↗

Spectroscopy of the extreme ultraviolet dayglow at 6.5A resolution - Atomic and ionic emissions between 530 and 1240A

EUV spectra (530-1500A) of the day airglow in up, down and horizontal aspect orientations have been obtained with 6.5A resolution and a limiting sensitivity of 5R from a rocket experiment. Below 834A the spectrum is rich in previously unobserved OII transitions connecting with 4S(0), 2D(0), and 2P(0) states. Recent broad-band photometric observations of geocoronal HeI 584A emission in terms of the newly observed OII emissions are shown. The OI 989A and OI 1304A emissions exhibit similar dependence on altitude and viewing geometry with the OI 989A brightness 1/15 that of OI 1340. Emission at 1026A is identified as geocoronal HI Lyman beta rather than OI multiplet emission and observed intensities agree well with model estimates. An unexpectedly high NI 1200/NI 1134A brightness ratio is evidence of a significant contribution from photodissociative excitation of N2 to the NI 1200A source function.

Gentieu, E. P.↗

Ice in the lunar polar regions

The idea that ice and other trapped volatiles exist in permanently shadowed regions near the lunar poles was proposed by Watson, Murray, and Brown (1961). It is reexamined in the present paper, in the light of the vast increase of lunar knowledge. The stability of the traps and the trapping mechanism are verified. Four potential sources of lunar H2O, namely (1) solar wind reduction of Fe in the regolith, (2) H2O-containing meteoroids, (3) cometary impact, and (4) (the least certain) degassing of the interior, can supply amounts of trapped H2O estimated in the range of 10 to the 16th to 10 to the 17th g. Two important destructive mechanisms have been identified: photodissociation of H2O molecules adsorbed on the sunlit surface and sputtering or decomposition of trapped H2O by solar wind particles. The effect of impact gardening is mainly protective. The question of the presence of H2O in the traps remains open; it can be settled by experiment.

Arnold, J. R.↗

Comparison of the Nimbus-4 BUV ozone data with the Ames two-dimensional model

A comparison is made of the first two years of Nimbus 4 backscattered ultraviolet (BUV) ozone measurements with the predictions of the Ames two dimensional model. The ozone observations used consist of the mixing ratio on the 1, 2, 5, and 10 mb pressure surfaces. The data are zone and time averaged to obtain seasonal means for 1970 and 1971 and are found to show strong and repeatable meridional and seasonal dependencies. The model used for comparison with the observations extends from 80 N to 80 S latitude and from altitudes of 0 to 60 km with 5 deg horizontal grid spacing and 2.5 km vertical grid spacing. Chemical reaction and photolysis rates are diurnally averaged and the photodissociation rates are corrected for the effects of scattering. The large altitude, latitude, and seasonal changes in the ozone data agree with the model predictions. Model predictions of the sensitivity of the comparisons to changes in the assumed mixing ratios of water vapor, odd nitrogen, and odd chlorine, as well as to changes in the ambient temperature and transport parameters are also shown.

Borucki, W. J.↗

Vibronic effects in the predissociation of the C/1/Pi/u state of C2N2

The partitioning of excess photochemical energy as a function of the vibrational energy of the state of C2N2 has been measured. Surprisal theory has been used to analyze the data and it shows that complete randomization does not occur before dissociation. The results are also inconsistent with the predictions of the quasidiatomic theory for photodissociation.

Miller, G. E.↗

Solar variability and ozone

Stratospheric temperature and concentration of ozone above 26 km, as measured by rocket-borne instruments, showed an increase from 1964 to 1969-70, and a decline between 1970 and 1975, closely following the solar cycle, which peaked in 1969 (+0.89 correlation at both 35 and 50 km). Similar correlations were found between the ozone density and the 10.7 cm solar radio flux (as measured by the Nimbus IV satellite), and between ozone column density and the Lyman-alpha flux, both observations being taken over the same 10 month period. A mechanism is hypothesized which would link solar flux variation with both changes in stratospheric temperature and concentration of ozone (which is produced by the photodissociation of stratospheric oxygen molecules by solar radiation in the ultraviolet wavelength region).

Callis, L. B.↗

Ultraviolet absorption spectrum of methylhydroperoxide vapor

The ultraviolet absorption cross sections of methylhydroperoxide, CH3OOH, have been measured over the wavelength range 210 nm to 350 nm at 294 K. It was concluded that solar photolysis is a dominant sink for tropospheric CH3OOH. For midlatitudes the photodissociation rate was estimated for 0 deg, for 30 deg, and for 70 deg zenith angles.

Molina, M. J.↗

Photo-sputtering of ice and hydrogen around Saturn's rings

It is noted that rocketborne UV spectroscopic measurements have shown that a dense cloud on atomic hydrogen surrounds Saturn which has been interpreted as being associated with the Saturn ring system. Several ring sources of atomic hydrogen have been proposed, but abundance and lifetime estimates require a source which is much more potent than those previously considered. An alternate mechanism is proposed which satisfies this source requirement and involves photodissociation of surface water molecules on the icy ring material. The source rate for this mechanism is within a factor of two of the required value and is within the experimental error of the measurement.

Carlson, R. W.↗

Presupernova models and supernovae

The present status of theories of presupernova stellar evolution and the triggering mechanisms of supernova explosions are reviewed. The validity of the single-star approximation for stellar core evolution is considered, and the central density and temperature of the stellar core are discussed. Attention is then given to the results of numerical models of supernova explosions by carbon deflagration of an intermediate mass star, resulting in the total disruption of the star; the photodissociation of iron nuclei in a massive star, resulting in neutron star or black hole formation; and stellar core collapse triggered by electron capture in stars of mass ranging between those of the intermediate mass and massive stars, resulting in neutron star formation despite oxygen deflagration. Helium and carbon combustion and detonation in accreting white dwarfs and the gravitational collapse triggered by electron-pair creation in supermassive stars are also discussed, and problems requiring future investigation are indicated.

Sugimoto, D.↗

Stratospheric ozone decrease due to chlorofluoromethane photolysis - Predictions of latitude dependence

A two-dimensional model is used to predict the 1990 reduction in ozone due to the chlorine compounds formed by chlorofluoromethane (CFM) photolysis when the CFM release rate is held constant at the 1975 value. The predicted globally averaged ozone reduction of 3.5% is similar to that predicted by one-dimensional models that did not include chlorine nitrate chemistry, and used lower values for the reactions rates of NO + HO2 yielding NO2 + OH and O3 + HO2 yielding OH + 2O2. When the 5.7 ppbv increase in chlorine compounds predicted by one-dimensional models to occur under steady-state conditions is simulated by the two-dimensional model, a 26% decrease in atmospheric ozone is predicted. The latitude dependence of the ozone reduction is discussed in terms of the relevant photochemical reaction and transport. The chemical reactions that most strongly influence the meridional dependence of the ozone depletion are identified as those associated with the reactions of chlorine monoxide and atomic oxygen, the recombination of ozone and atomic oxygen, and the photodissociation of molecular oxygen.

Borucki, W. J.↗

Production of OH from photolysis of HOCl at 307-309 nm

Laser-induced fluorescence has been used to measure the amount of OH produced in the laser photolysis of HOCl at 310 nm. The HOCl was generated by the Cl2O + H2O and by the HCl + Cl2O reactions. The laser technique samples OH on a microsecond time scale so that secondary radical reactions cannot contribute significantly to the observed signals. The fluorescence signals were calibrated with O3-H2O mixtures, the reactions O3 + h(nu) yields O(1D) + O2 and O(1D) + H2O yields 2OH yielding known amounts of OH. The value for the absorption cross section of HOCl at 310 nm has been determined to be 6 x 10 to the -20th sq cm, assuming K(eq) = 0.082 for the Cl2O + H2O yields 2HOCl system and assuming unit quantum yield for the production of OH. The present investigation further supports earlier experimental work concluding that HOCl will photodissociate rapidly and will not be an important holding tank for chlorine in the stratosphere. These results are in disagreement with theoretical calculations of the UV absorption spectrum of HOCl in the 300-350-nm wavelength region.

Molina, M. J.↗

The ultraviolet dayglow. I - Far UV emissions of N and N2

Far ultraviolet rocket spectra of N I and N2 dayglow emissions have been analyzed by using AE-E photoelectron spectra, laboratory-measured excitation cross sections, and photochemical models of atomic nitrogen. A self-consistent picture of both optically thick and thin emission features is found by using a model in which the principal production mechanism for N I 1200-A and 1493-A photons is photodissociative excitation of N2. The aeronomic data require that 50-70% of the excited 4 P atoms produced dissociatively have velocities within the Doppler core of the ambient nitrogen atoms, contrary to the expectation that those atoms are produced with large excess kinetic energy. The derived atomic nitrogen density has a maximum density of 2.7 x 10 to the 7th per cu cm at 170 km, a value that is within 40% of that from recent models of odd nitrogen photochemistry.

Meier, R. R.↗

Neutral cometary atmospheres. II - The production of CN in comets

Brightness profiles of the CN (0-0) band at 3883 A have been constructed from spectrograms of comets Bennett (1979 II) and West (1976 VI). The subsequent analysis of these profiles shows that the parent molecule of CN had a radial scale length of (2.19 plus or minus 0.07) x 10 to the 4th r (H-squared), in kilometers. This, combined with current theories as well as photochemistry, is consistent with production by simple photodissociation of HCN. The rather random variation of the radial scale length for the apparent decay of CN is indicative not of a true decay scale length, but of the fact that no steady state in the CN parent production rate is achieved for the time scale necessary to build up the observed profile. A revision of the average CN production law with heliocentric distance from published photometry indicates an r(H to the -2nd) law for comet West out to at least 2.555 AU. This implies that the vaporization of this comet was controlled by some species more volatile than water. Based on this and other evidence, CO2 is suggested, but even more volatile molecules like CO cannot be ruled out.

Combi, M. R.↗

Upper atmosphere modifications due to chronic discharges of water vapor from space launch vehicle exhausts

The influences of transport, photodissociation, and frequency of injection on the global redistribution of water deposited in the earth's upper atmosphere by repeated launches of large rockets are investigated. Measurable environmental effects of the injected water are found to occur when the mesospheric water vapor mixing ratio exceeds 100 ppmv, which occurs over areas of order 20,000 sq km in connection with possible future Satellite Power System activities. These effects include (1) a 50% reduction in D-region ionization due to screening of L alpha radiation by water; (2) a 50% reduction of D-region ionization as a result of converting NO(+) to water cluster ions which possess more rapid recombination rates; (3) a doubling of OH concentrations below 100 km; and (4) a global doubling of nighttime E-region ionization due to L alpha and L beta radiations geocoronally scattered by atomic hydrogen released by photolysis of H2O. Mixing ratios of 1,000 ppmv necessary for the maintenance of clouds at the mesopause are reached only over areas of order 200 sq km.

Forbes, J. M.↗