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At least 55 records · Page 3

Temperature dependence of the NO + O3 reaction rate from 195 to 369 K

The temperature dependence of the NO + O3 reaction rate was examined by means of the fast flow technique. Several different experimental conditions and detection schemes were employed. With excess NO or excess O3, NO2 chemiluminescence was monitored. In addition, with excess O3, NO was followed by fluorescence induced by an NO microwave discharge lamp. The results of the three independent sets of data are compared and found to agree within experimental error, indicating the absence of secondary chemistry which might complicate the kinetics. The data exhibit curvature on an Arrhenius plot; however, the simple Arrhenius expression k = (2.6 + or - 0.8) x 10 to the -12th exp(-1435 + or - 64/T) cu cm/molecule s is an adequate description for T between 195 and 369 K. This result is compared to earlier determinations.

Michael, J. V.↗

In situ stratospheric ozone measurements by long path UV absorption - Developments and interpretation

A high-sensitivity, in situ UV absorption ozone sensor has been developed for use in the stratosphere. The instrument couples 254-nm radiation from a low-pressure mercury discharge lamp into a 40-pass White cell to attain a high-sensitivity ozone absorption measurement. Preflight/postflight laboratory tests utilizing an ozone source coupled to a laboratory UV ozone photometer in a fast-flow system as well as in-flight diagnostics verify the successful operation of the instrument. Evidence is presented to verify that in situ UV absorption ozone photometers can measure stratospheric ozone with better than 3 percent precision and 5 percent accuracy, provided proper attention is given to both the thermal field surrounding the gondola and the ambient pressure measurements. Ozone data are compared with modeled profiles in the 28- to 40-km region. An assessment of the disagreement between observations and modeled profiles is given along with suggestions for future experiments designed to constrain photochemical models.

Weinstock, E. M.↗

Rate constants for the quenching of metastable O2 (1Sigma g +) molecules

The O2 (1Sigma g +) rates for CO2, H2, N2, Cl2, CO, O3, and 2,3 DMB-2 are determined by monitoring the 762-nm emission in a fast-flow-discharge chemiluminescence detection system (Leu, 1984; Leu and Smith, 1981). The results are presented in tables and graphs and briefly characterized. The rate constants (in cu cm/s x 10 to the -16th) are 4600 + or - 500 for CO2, 7000 + or - 300 for H2, 17 + or - 1 for N2, 4.5 + or - 0.8 for Cl2, 45 + or - 5 for CO, 220,000 + or - 30,000 for O3, and 6000 + or - 100 for 2,3 DMB-2. The temperature dependence of the CO2 and O3 quenching reactions at 245-362 K is found to be negligible.

Kwang, Y. C.↗

Model ion abundances for Comet Halley

A computer model for comet comae was applied to predict ion abundances for comet Halley, assuming that the volatile component of the nucleus is 85% water and that the remaining volatile molecules are composed of carbon, nitrogen, oxygen, and sulfur. Model parameters such as heliocentric distance, size, and albedo are chosen to be consistent with the 13 to 14 March 1986 encounter of Giotto with the comet. Photoprocesses, gas-phase chemical kinetics, coma energy balance including a separate electron temperature, multifluid hydrodynamics with a transition to free molecular flow, fast streaming atomic and molecular hydrogen, and counter and cross streaming of species in the coma-solar wind interaction are taken into consideration. A comparison of the model results with data from the ion mass spectrometer at 6000 and 1500 km from the nucleus shows good agreement. Implications of the coma physics and chemistry are discussed.

Huebner, W. F.↗

Laboratory studies of sticking coefficients and heterogeneous reactions important in the Antarctic stratosphere

Laboratory studies of sticking coefficients of H2O, HCl, Cl2, and HNO3 on ice and heterogeneous reactions of ClONO2 with ice or HCl/ice have been performed in a fast flow reactor. A quadrupole mass spectrometer with electron impact ionization was used as a detector. Measured sticking coefficients are: 0.3 (+0.7, -0.1) for H2O, 0.4 (+0.6, -0.2) for HCL, less than 0.0001 for Cl2, and 0.3 (+0.7, -0.1) for HNO3 at 200 K. The reaction probability of ClONO2 on ice was found to be 0.06 (+ or - 0.03) while HOCl was observed as a sole product in the gas phase. With HCl present in ice, the reaction probability of ClONO2 is greatly enhanced, approaching 0.27 (+0.73, -0.13) while molecular chlorine was found to be the major product in the gas phase. Another reaction product was nitric acid which remained in the solid phase. Since the polar stratospheric clouds contain ice particles or possibly HCl/ice particles on the surface, the present results should be a major factor in producing the observed springtime ozone depletion in the Antarctic stratosphere.

Leu, Ming-Taun↗

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗

FAST: A multi-processed environment for visualization of computational fluid

Three dimensional, unsteady, multizoned fluid dynamics simulations over full scale aircraft is typical of problems being computed at NASA-Ames on CRAY2 and CRAY-YMP supercomputers. With multiple processor workstations available in the 10 to 30 Mflop range, it is felt that these new developments in scientific computing warrant a new approach to the design and implementation of analysis tools. These large, more complex problems create a need for new visualization techniques not possible with the existing software or systems available as of this time. These visualization techniques will change as the supercomputing environment, and hence the scientific methods used, evolve ever further. Visualization of computational aerodynamics require flexible, extensible, and adaptable software tools for performing analysis tasks. FAST (Flow Analysis Software Toolkit), an implementation of a software system for fluid mechanics analysis that is based on this approach is discussed.

Bancroft, Gordon V.↗

Photodissociation of the hydroxyl radical (OH) at 157 nm

The photodissociation of the OH radical was studied at 157 nm via the detection of the product H atoms with the resonance fluorescence technique. OH radicals were produced in a fast-flow cell from the reaction between H and NO2 and subsequently photodissociated by an excimer laser operating on the F2 emission. The quantum yield for photodissociation of OH was measured to be 1.10 + or - 0.28. The photodissociation cross section was calculated to be 6.6 x 10 to the -18th sq cm (+ or - 25 percent).

Cody, R. J.↗

Nonlocal thermodynamic equilibrium effects of vibrationally excited NO

Results are presented of a laboratory investigation of the vibrational distribution of NO produced in the reaction between O(3P) and NO2(X 2A1). To minimize vibrational quenching, the experiments were performed in a fast-flow system. The production of NO(X) radicals was monitored with laser-induced fluorescence. It was found that the NO vibrational population ratio measured correlates well with the earlier observation of high vibrational excitation in O2.

Moralejo, C.↗

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗

Relative timing of substorm features in MHD simulations

An investigation of the temporal sequence of substorm phenomena based on three dimensional MHD (magnetohydrodynamic) simulations of magnetic reconnection and plasmoid formation is presented. The investigation utilizes a spatially localized resistivity model which leads to a significantly faster evolution than found in previous investigations. The analysis of the results concentrates on substorm features that have received considerable attention in the past. The formation of magnetic neutral lines, the occurrence of fast flows directed both earthward and tailward, and the magnetic field changes leading to the formation of the substorm current wedge, and to the depolarization of the magnetic field earthward of the reconnection region and its dependence on the spatial distribution of resistivity, are discussed. These phenomena are seen as an integral part of the nonlinear evolution of the three dimensional tearing instability.

Hesse, Michael↗

Topological structure of the magnetotail as a function of interplanetary magnetic field direction

Magnetic reconnection between the interplanetary magnetic field (IMF) and the geomagnetic field is thought to play a major role in the transfer of solar wind momentum and energy to the magnetosphere. As the angle between the IMF and the geomagnetic field is changed at the bow of the magnetosphere, the topological record of the location of the reconnection region should be recorded in the magnetosheath and on the magnetopause along the flanks of the tail, because the super fast flow freezes strong magnetic gradients formed in the bow reconnection regions into the plasma downstream. In this report, we present results from a three-dimensional, magnetohydrodynamic (MHD), global numerical simulation code for the location of the separatrix between unconnected IMF magnetosheath field lines and reconnected field lines which penetrate the magnetopause and connect to the polar ionosphere. The angle between the IMF direction and the line where the separatrix crosses the magnetopause is shown to be a sensitive function of the IMF clock angle. We also explain how this behavior can be used to derive an approximate relation for the dependence of the cross-polar voltage on the IMF clock angle. We conclude with a note of caution concerning the importance of physical boundary conditions in magnetoplasma simulations.

Fedder, J. A.↗

SAR investigations of glaciers in northwestern North America

The objective of this project was to investigate the utility of satellite synthetic aperture radar (SAR) imagery for measurement of geophysical parameters on Alaskan glaciers relevant to their mass balance and dynamics, including: (1) the positions of firn lines (late-summer snow lines); (2) surface velocities on fast-flowing (surging) glaciers, and also on slower steady-flow glaciers; and (3) the positions and changes in the positions of glacier termini. Preliminary studies of topography and glacier surface velocity with SAR interferometry have also been carried out. This project was motivated by the relationships of multi-year to decadal changes in glacier geometry to changing climate, and the probable significant contribution of Alaskan glaciers to rising sea level.

Lingle, Craig S.↗

Geostatistical approaches to interpolation and classification of remote-sensing data from ice surfaces

Geostatistical methods for interpolation and extrapolation techniques are used in glaciological data analysis. The results of a program involving the mapping of the Antarctica from satellite radar altimeter data are discussed. A combination of high and low resolution techniques was applied in the analysis of the Bering Glacier (Alaska). The global positioning system (GPS) located video data collected from small aircraft and the ERS-1 synthetic aperture radar (SAR) images were used. From the perspective of SAR data analysis, the Bering Glacier surge was the opportunity to characterize the surface of fast flowing ice and the rapid changes in the surface roughness.

Herzfeld, Ute Christina↗

The role of impulsive particle acceleration in magnetotail circulation

Recent results from investigations carried out using the active magnetospheric particle tracer explorer/ion release module (AMPTE/IRM) satellite and International Sun-Earth Explorer (ISEE) show that bursty, near-neutral sheet fast flows are an important part of the transport in the near-earth tail. The results related to such flows are reviewed, and information is presented on their relation to the average plasma sheet characteristics and substorms. The average ion density, temperature and flow variability in the quiet inner plasma sheet exhibit a spatial dependence which suggests a dependence on Bursty Bulk Flows (BBFs). The energy and flux transport in the tail is discussed and it is stated that BBFs are responsible for such transport. The tailward progression of activity is considered.

Angelopoulos, V.↗

Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at high latitudes in winter and early spring, even at temperatures too warm for Polar Stratospheric Clouds (PSCs) to form or in regions where nucleation of PSCs is sparse. This is particularly true under elevated sulfuric acid loading, such as that after the eruption of Mt. Pinatubo. Comparisons between our results and those presently available have also been made.

Zhang, Renyi↗

Heterogeneous Interactions of ClONO2 and HCl with Sulfuric Acid Tetrahydrate: Implications for the Stratosphere

The reaction probabilities for ClONO2+H2O- HOCl + HNO3 and ClONO2+ HCl Cl2 +HNO3 have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4-4H2O)surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lower stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial pressure at a given temperature, and decrease with increasing temperature at a given H2O partial pressure, as the SAT changes from the H2O-rich form to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(sub 1) approx. = -0.01 and gamma(sub 2) greater or equal to 0.1, whereas the values for H2SO4-rich SAT decrease by more than 2 orders of magnitude. At low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a coverage of the order of a tenth of a monolayer (approx. = 10(exp 14) molecules/sq cm); H2SO4-rich SAT films take up 2 orders of magnitude less HCl (les than 10(exp 12) molecules/sq cm). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The data reveal that frozen stratospheric sulfate aerosols may play an important role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratospheric cloud particles.

Zhang, Renyi↗

Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

Zhang, Renyi↗