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At least 307 records · Page 17

A kinetics study of the homogeneous and heterogeneous components of the HCl + ClONO2 reaction

The kinetics of the reaction HCl + ClONO2 to Cl2 + HNO3 were investigated at 298 K using a flow reactor with FTIR analysis to assess the importance of this reaction for stratospheric chemistry. The observed reaction was characteristic of a heterogeneous process; an upper limit of 5 x 10 to the -18th cu cm/molecule per s was obtained for the homogeneous gas phase rate constant. From calculations of the first order wall rate constant, estimates were made of the reaction rate on stratospheric aerosols. Because both HCl and ClONO2 need to be adsorbed on the particle surface, the reaction will be of negligible importance under most stratospheric conditions.

Friedl, Randall R.↗

Balloon-borne cryogenic spectrometer for measurement of lower stratospheric trace constituents

A liquid-nitrogen cooled, multidetector Fourier transform spectrometer has been constructed to measure minor stratospheric constituents via high resolution, earth-limb emission spectroscopy from a balloon-borne platform. Cryogenic cooling, combined with the use of extrinsic silicon photoconductor detectors cooled to liquid-helium temperature, allows the detection of weak emission features of gaseous species. The spectrometer has two basic scan modes: the first mode records the continuous spectrum from 650-2100/cm with 0.2/cm resolution; the second simultaneously records four preselected narrow intervals (about 175/cm bandpass each) with 0.02/cm resolution, unapodized. Filtering of the interferogram signal is done by real-time, digital signal processing. The most important feature of this flat mirror Michelson system, with respect to remote balloon-borne operation, is the dynamic alignment system which maintains the relative parallelism of the two flat reflectors of the interferometer. Species identified to date in data obtained during a Nov. 6, 1984, flight include: CO2, O3, H2O, CH4, HNO3, N2O, NO2, NO, CCl3F (Freon-11) and CF2Cl2 (Freon-12).

Brasunas, J. C.↗

Infrared spectroscopy of the lower stratosphere with a balloon-borne cryogenic Fourier spectrometer

The IR limb emission of the lower stratosphere has been measured using a balloon-borne liquid nitrogen-cooled Michelson interferometer with liquid helium-cooled Si:Ga detectors. Portions of the thermal emission spectrum have been recorded between 650 and 2000/cm with an unapodized spectral resolution of 0.03/cm. This is the highest spectral resolution limb emission thus far obtained. A preliminary description is given of these data along with a discussion of the significant features. Species identified to date include CO2, O3, CFCl3, CF2Cl2, H2O, CH4, HNO3, N2O, NO2, and ClONO2. A tentative identification is made for NO, representing the first direct spectroscopic detection of NO in emission.

Kunde, Virgil G.↗

The use of atmospheric measurements to constrain model predictions of ozone change from chlorine perturbations

Atmospheric photochemistry models have been used to predict the sensitivity of the ozone layer to various perturbations. These same models also predict concentrations of chemical species in the present day atmosphere which can be compared to observations. Model results for both present day values and sensitivity to perturbation depend upon input data for reaction rates, photodissociation rates, and boundary conditions. A method of combining the results of a Monte Carlo uncertainty analysis with the existing set of present atmospheric species measurements is developed. The method is used to examine the range of values for the sensitivity of ozone to chlorine perturbations that is possible within the currently accepted ranges for input data. It is found that model runs which predict ozone column losses much greater than 10 percent as a result of present fluorocarbon fluxes produce concentrations and column amounts in the present atmosphere which are inconsistent with the measurements for ClO, HCl, NO, NO2, and HNO3.

Douglass, Anne R.↗

Wheat production in controlled environments

Conditions are optimized for maximum yield and quality of wheat to be used in a controlled environment life support system (CELSS) in a Lunar or Martian base or a spacecraft. With yields of 23 to 57 g/sq m/d of edible biomass, a minimum size for a CELSS would be between 12 and 30 sq m per person, utilizing about 600 W/sq m of electrical energy for artificial light. Temperature, irradiance, photoperiod, carbon dioxide levels, humidity, and wind velocity are controlled in growth chambers. Nutrient solutions (adjusted for wheat) are supplied to the roots via a recirculating system that controls pH by adding HNO3 and controlling the NO3/NH4 ratio in solution. A rock-wool plant support allows direct seeding and densities up to 10,000 plants sq m. Densities up to 2000 plants/sq m appear to increase seed yield. Biomass production increases almost linearily with increasing irradiance from 400 to 1700 micromol/sq m/s of photosynthetic photon flux, but the efficiency of light utilization decreases over this range. Photoperiod and temperature both have a profound influence on floral initiation, spikelet formation, stem elongation, and fertilization.

Salisbury, Frank B.↗

Acid dew and the role of chemistry in the dry deposition of reactive gases to wetted surfaces

A formalism is developed to describe the dry deposition of soluble reactive gases to wetted surfaces in terms of the relevant meteorological conditions, the surface roughness, the total amount of liquid water present on the surface, the rate of accumulation of this water, and the species' solubility and reactivity in the surface water. This formulation is then incorporated into a model designed to simulate the generation of acidic dew from the deposition of HNO3, SO2, S(IV) oxidants, H2O2, and O3. Similar to the observations of dew in the continental U.S., the model generates a dewdrop pH of about 4 by the end of the night; the pH can rapidly fall to toxic levels due to rapid evaporation after sunrise. Relatively low deposition velocities are predicted for the SO2 and O3 because of their lower solubilities and hence larger surface resistances than those of the other oxidants. Because the chemical lifetime of the SO2 in the dew is influenced by the atmospheric levels of H2O2, O3, and SO2, the SO2 deposition velocity is a strong function of these species' atmospheric abundances.

Chameides, William L.↗

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Tolbert, Margaret A.↗

Infrared measurements of several nitrogen species above the South Pole in December 1980 and November-December 1986

This paper reports the results of the determinations of total column amounts of HNO3 for December 1980 and November 1986, and NO and NO2 for November-December 1986, deduced from ground-based high-resolution IR solar absorption spectra recorded from the Amundsen-Scott South Pole Station. The measurements were obtained shortly after the austral spring ozone minimum and define, for the first time, the ambient levels of these nitrogen species immediately following the break up of the polar vortex.

Murcray, F. J.↗

The ozone hole - The role of polar stratospheric cloud particles

The role of polar stratospheric clouds in the formation of the Antarctic ozone hole is considered. Several researchers have suggested that the decrease in ozone over Antarctica is related to the polar stratospheric clouds (PSCs) which had been observed in the antarctic winter stratosphere. Some of the pertinent characteristics of polar stratospheric clouds are discussed, and it is shown how these clouds may participate in the ozone destruction process. The satellite data for PSCs is analyzed, and statistical information regarding the number and maximum extinctions of these clouds is presented. Evidence that the polar stratospheric clouds are composed of frozen nitric acid is considered. It is suggested that the evaporation of the clouds, in late August and September, will release HOCl and HNO3 to the environment. This could be followed by the photodissociation of HOCl to OH and Cl, which would very effectively destroy ozone. However, the ozone destruction mechanism could be halted when enough of the evaporated nitric acid is photolized.

Hamill, Patrick↗

Airborne lidar observations of Arctic polar stratospheric clouds - Indications of two distinct growth stages

Airborne lidar observations of Arctic polar stratospheric clouds (PSCs) during January 1984 and January 1986 show contrast suggestive of two distinct PSC growth stages delineated by the frost-point temperature. Results obtained at temperatures 2-6 K above the frost point indicate a stage of significant, but limited, particle growth such as proposed in recent models of PSC formation by co-deposition of HNO3 and H2O vapors. Results obtained at a temperature near the frost point indicate the formation of somewhat larger crystalline particles.

Poole, Lamont R↗

Response function of a tunable diode laser spectrometer from an iterative deconvolution procedure

A deconvolution procedure commonly used for resolution enhancement of spectra has been applied to the determination of the response function of a tunable diode laser spectrometer. The method is sufficiently fast and simple for routine application when correcting for nonnegligible instrumental broadening. Absolute linestrengths of CH4 in the 1327/cm region and line positions of HNO3 in the 1335/cm region, measured with the aid of the deconvolution technique, are reported here.

May, Randy D.↗

Infrared measurements of column abundances of several trace gases in the Antarctic atmosphere

Atmospheric emission measurements were made in 1978 from an LC 130 aircraft from Point Mugu, CA, to McMurdo Station, Antarctica, and from McMurdo over the Antarctic continent on several different flights. These included a number of flights over the South Pole. In December 1980, infrared solar spectra were obtained from the ground at South Pole Station. Infrared solar spectra were also obtained from South Pole during late November and early December of 1986. These latter measurements were extended to cover additional spectral regions to obtain column densities of a number of additional constituents. The results obtained from these measurement series are reviewed and, where measurements were made during both periods, compared. Spectral absorption or emission features due to HNO3, NO, NO2, HCl, (H-16)2O, (H-18)2O, HDO, CH4, and N2O were used to obtain data on the total column abundances for these compounds.

Murcray, F. J.↗

Polar stratospheric clouds and the Antarctic ozone hole

A theoretical model for the formation and growth of polar stratospheric clouds (PSCs) has been developed. Results for the calculated temperature dependence of optical backscattering are found to agree well with values obtained during two Arctic airborne-lidar experiments. Results for PSC formation in Antarctica show that at the 70-mbar level, about 80 percent of the HNO3 and about 30 percent of the H2O vapor available may be sequestered in relatively large PSC particles at a temperature near 189 K.

Poole, Lamont R.↗

ClO and O3 stratospheric profiles - Balloon microwave measurements

Stratospheric ClO and O3 vertical profiles were measured at 32-deg N in May 1985 and October 1986. The ClO profiles and diurnal variation are in general agreement with theory, but have somewhat less midday ClO near 34 km. Measured 35-45 km O3 is larger than theoretical, and no stratospheric O3 diurnal variation was observed, as expected. HNO3 was detected, and an H2O2 upper limit was obtained.

Waters, J. W.↗

Balloon borne Antarctic frost point measurements and their impact on polar stratospheric cloud theories

Balloon-borne frost point measurements were performed over Antarctica during September-October 1987 as part of the NOZE II effort at McMurdo. The results show water mixing ratios on the order of 2 ppmv in the 20 km region, suggesting that models of the springtime Antarctic stratosphere should be based on approximately 2 ppmv water vapor. Evidence indicating that some PSCs form at temperatures higher than the frost point in the 15 to 20 km region is discussed. This supports the binary HNO3-H2O theory of PSC composition.

Rosen, James M.↗

Lidar observations of Arctic polar stratospheric clouds, 1988 - Signature of small, solid particles above the frost point

The paper presents recent (January 1988) Arctic airborne lidar data which suggest that Type I polar stratospheric clouds (PSCs) are composed of small solid particles with radii on the order of 0.5 micron. PSCs were observed remotely in the 21-24 km altitude range north of Greenland during a round-trip flight from Andenes, Norway on January 29, 1988, aboard the NASA Wallops Flight Facility P-3 Orion aircraft. Synoptic analyses at the 30-mb level show local temperatures of 191-193 K, which are well above the estimated frost point temperature of 185 K; this suggests that the PSCs were probably of the binary HNO3-H2O (Type I) class.

Poole, L. R.↗

Influence of polar stratospheric clouds on the depletion of Antarctic ozone

Precipitation of nitrate in polar stratospheric clouds (PSCs) can provide a significant sink for Antarctic stratospheric odd nitrogen. It is argued that the depth of the Ozone Hole is sensitive to the occurrence of temperatures below about 196 K. An increase in the prevalence of temperatures below 196 K would enhance ozone loss by increasing the spatial extent and persistence of PSCs, and by decreasing the level of HNO3 that remains following PSC evaporation. Concentrations of halogen gases in the 1960s and earlier were insufficient to support major ozone loss, even if thermal conditions were favorable.

Salawitch, Ross J.↗

Pressure broadening of NO2, CF2Cl2, HDO and HOOH by O2 and N2 in the millimeter wave region

The pressure-broadening coefficients of four molecules of atmospheric significance (NO2, CF2Cl2, HDO and HOOH) have been measured in the millimeter wave region. For each species, two transitions near 230 GHz were broadened by both N2 and O2, for a total of 16 different pressure-broadening measurements. Intercomparisons among the results of these measurements, as well as recent more extensive measurements on HNO3, are considered.

Goyette, Thomas M.↗