Engineering Papers⌕ Search

Engineering topics

Kaye, Jack A.

Publications and source records attributed to Kaye, Jack A..

30 records · Page 2

Three dimensional simulation of spatial and temporal variability of stratospheric hydrogen chloride

Spatial and temporal variability of atmospheric HCl columns are calculated for January 1979 using a three-dimensional chemistry-transport model designed to provide the best possible representation of stratospheric transport. Large spatial and temporal variability of the HCl columns is shown to be correlated with lower stratospheric potential vorticity and thus to be of dynamical origin. Systematic longitudinal structure is correlated with planetary wave structure. These results can help place spatially and temporally isolated column and profile measurements in a regional and/or global perspective.

Kaye, Jack A.↗

Vertical, meridional, seasonal, and local time dependence of non-LTE effects in stratospheric NO and implications for infrared remote sensing

Calculations have been carried out on possible nonlocal thermodynamic equilibrium (non-LTE) effects previously suggested for stratospheric nitric oxide (NO) associated with the direct photochemical production of vibrationally excited NO by the processes NO2 + hv yields NO(v) + O and O + NO2 yields NO(v) + O2. The calculations, which make use of improved calculations of the NO vibrational state distribution from NO2 photolysis, are carried out as a function of altitude and latitude for a variety of seasons and local times. Non-LTE effects on the order of 30 percent for v = 1 are obtained, maximizing in the middle stratosphere over the equator. The results of the calculations suggest that incorporation of the non-LTE effect into the retrieval algorithm for NO from infrared thermal emission measuring instruments on the Upper Atmosphere Research Satellite will need to be done carefully if correct distributions and variations of NO with altitude, latitude, season, and local time are to be obtained.

Kaye, Jack A.↗

The use of assimilated stratospheric data in constituent transport calculations

A stratospheric assimilation system has been developed, which generates wind data that is consistent with the geopotential height (and temperature) field and the primitive equations in the general circulation model. This paper reports the first known calculations to use data from an assimilation to calculate constituent transport in the stratosphere. Nitric acid (NHO3) during the Limb IR Monitor of the Stratosphere (Gille et al., 1984) period is studied. The high-latitude time variance of the HNO3 is accurately captured. These studies suggest that data from an assimilation process offers tremendous potential for studying stratospheric dynamics, constituent transport, and chemistry.

Rood, Richard B.↗

Chemistry and transport in a three-dimensional stratospheric model - Chlorine species during a simulated stratospheric warming

The distributions in the stratosphere of a variety of chemical species were calculated for a 6-day period during the February 1979 stratospheric major warming, using winds derived from a spectral forecast model which included O(x), NO(x), HO(x), and ClO(x) chemistries as well as longitudinally varying reaction rate coefficients and photolysis rates for these molecules. The results obtained indicate a particular importance of chemistry and transport for the Cl-containing species ClO, ClONO2, HCl, and HOCl. Dynamical effects dominate the variability of HCl, while diurnal effects dominate that of ClONO2 and ClO. The effects of strong planetary wave activity may be seen in terms of large longitudinal variability of the total HCl and ClONO columns in the stratosphere; in the middle and high northern latitudes, it is sufficiently large to exceed the diurnal variability of the column.

Kaye, Jack A.↗

On the possible role of the reaction O + HO2 - OH + O2 in OH airglow

Experimental data on the so-called 'perhydroxyl' reaction O + HO2 - OH + O2 by which vibrationally excited OH is produced in the upper atmosphere are briefly reviewed. Both isotopic labeling studies and studies on the temperature dependence of the rate constant and the possible importance of its inverse are considered. The implication of the results for analysis of OH airglow data are emphasized. Some additional results on the dynamics of reactions related to OH airglow which may affect interpretation of OH emission measurements are summarized.

Kaye, Jack A.↗

Nonlocal thermodynamic equilibrium effects in stratospheric NO and implications for infrared remote sensing

It is shown that the vibrational state population of stratospheric nitric oxide (NO) could be substantially different from that expected on the basis of LTE. Deviations from LTE may arise because stratospheric NO can be photochemically produced from NO2 with several vibrational quanta. Model calculations suggest that the population of NO(v = 1) could be some 30 percent above that expected from LTE at 30 km, with smaller enhancements above and below. Substantially larger enhancements are predicted for NO(v = 2). This result is shown to have important implications for NO determination by remote sensing of IR emission. Data needed for the quantification of these effects are enumerated.

Kaye, Jack A.↗

Mechanisms and observations for isotope fractionation of molecular species in planetary atmospheres

Chemcial and physical processes which may give rise to isotope fractionation of molecular species in the atmospheres of both earth and other planets are reviewed, along with observations of isotopically substituted molecules in planetary atmospheres. Mechanisms for production of isotope fractionation considered include atmospheric escape and the effect of isotope substitution on equilibrium constants (including those of phase changes), photolysis rates, and chemical reaction rates. The isotopes considered for compounds in the terrestrial atmosphere include D, T, C-13, C-14, N-15, O-18, and S-34. Compounds for which data about isotopic composition in the terrestrial atmosphere are summarized include CO, CO2, O3, N2O, NH3, SO2, H2S, H2O, H, H2, and CH4. Planetary atmospheres discussed include those of Venus, Mars, Jupiter, Saturn, Uranus, and Titan; isotopes reviewed are D, C-13, N-15, and O-18. Suggestions for additional research in the area of isotopically substituted molecules in atmospheres are offered.

Kaye, Jack A.↗

Analysis of the effects of zonal averaging on reaction rate calculations in two-dimensional atmospheric models

The usual assumption by which chemical reaction rates are calculated in two-dimensional atmospheric models is by using a product of zonal means of rate coefficients and constituent concentrations rather than the rigorous zonal mean of the corresponding products. This assumption has been tested for the reactions O + NO2 yields NO + O2 and NO + O3 yields NO2 + O2 using mapped limb infrared monitor of the stratosphere data from the Nimbus 7 satellite and found to be quite satisfactory for winter 1979 at 60 deg N in the upper stratosphere. Relative differences between the two-dimensional averaged rate and the more rigorous rate, calculated from the full, longitudinally varying temperatures and mixing ratios, were small (usually below 5 percent) and exceeded 15 percent only during times of strong dynamical activity. At those times or locations where stratospheric circulation is primarily zonal, the two averages agreed to within a few percent.

Kaye, Jack A.↗

Nitric acid forecast experiments

Results of two three-dimensional forecasts of the time evolution of the distribution of HNO3 in the stratosphere are reported. The first is for the February 1979 stratospheric warming, and the second is for a period in March, 1979 when the relative importance of photochemistry and dynamics is thought to be rapidly changing. The zonal mean results of the model calculations are in general qualitative agreement with the LIMS HNO3 observations. However, the calculated three-dimensional fields show significant differences from the observations. The results provide insight into what must be done to form a successful constituent forecast model and provide information on the modeling technique and the self-consistency of the observed dynamical and constituent fields.

Rood, Richard B.↗

An intercomparison of nitrogen-containing species in Nimbus 7 LIMS and SAMS data

Odd-nitrogen chemistry and transport are analyzed using a two-dimensional model and Nimbus 7 data. The Nimbus 7 data include: measurements of O3, NO2, HNO3, H2O, and temperature by the LIMS instrument; N2O, CH4, and temperature measurements by the SAMS instrument; and O3 data from the SBUV instrument. The characteristics of the two-dimensional model used in the study, a modified Guthrie et al. (1984) model, are described. NO2 and HNO3 are calculated using the two-dimensional model, and the computed data are compared with the LIMS NO2 and HNO3 measurements. The model uncertainties are computed based on the photochemical equilibrium assumption, and the role of stratospheric dynamics in determining NO2 and HNO3 is discussed. It is observed that there is good correlation between the LIMS and model data in the upper stratosphere; however, the data do not correspond in the lower stratosphere. The effect of nitrogen sources, such as lightning, on the stratospheric odd nitrogen distribution is examined.

Jackman, Charles H.↗

Comment on 'Heavy ozone in the stratosphere'

It is suggested that the factor-of-two difference in ozone formation rate constants derived by Bates (1986) can also be explained by the omission of standard correction factors from the rate expression. Proper accounting for the fact that isotope exchange and recombination reactions share a common energized collision complex (which can decay by dissociation to products isotopically distinct from the original reactants) eliminates the anomalous dependence of the rate constant on the isotopic composition of the reactants and products through their symmetry numbers. In a reply, Bates argues that symmetry effects in association do not lead to enhancement of the total heavy ozone abundance.

Anderson, Stuart M.↗

Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

Stolarski, Richard S.↗