Search NASA⌕ Search

Engineering topics

Margitan, J. J.

Publications and source records attributed to Margitan, J. J..

At least 55 records · Page 3

In Situ Measurements of CLO at Mid-Latitudes: Is there an Effect from Mt. Pinatubo?

Observations of ClO from 20 to 60 deg N made before and after the eruption of Mt. Pinatubo are compared for changes which may result from increased sulfate aerosol surface area. Using ozone as a vertical coordinate and examining data at similar latitudes and seasons, elevated abundances of ClO are found at low latitudes (20 to 30 deg N), an effect which decreases with increasing latitude. For the flights compared, there appear to be no differences, within the uncertainty of the measurements, at latitudes poleward of 40 deg N. These results are consistent with the idea that the hydrolysis of N2O5 on sulfate aerosols becomes saturated at moderate aerosol loadings.

Avallone, L. M.↗

Ozone loss inside the northern polar vortex during the 1991 - 1992 winter

Measurements made in the outer ring of the northern polar vortex from October 1991 through March 1992 reveal an altitude-dependent change in ozone, with a decrease at the bottom of the vortex and a substantial increase at the highest altitudes accessible to measurement. The increase is the result of ozone-rich air entering the vortex, and the decrease reflects ozone loss accumulated after the descent of the air through high concentrations of reactive chlorine. The depleted air that is released out of the bottom of the vortex is sufficient to significantly reduce column ozone at mid-latitudes.

Proffitt, M. H.↗

Polar stratospheric cloud processed air and potential vorticity in the Northern Hemisphere lower stratosphere at mid-latitudes during winter

The present study compares small-scale (less than 100 km) features in ER-2 measurements of ClO, O3, H2O, N2O, and NO(y) outside the lower stratospheric Arctic vortex of 1988-1989 with features on potential vorticity maps from ECMWF. The potential vorticity maps are obtained from T106 analyses and forecasts. Some of the plots were truncated to lower resolution (T63 or T42) which smooths out the finer-scale structure. Comparison of these lower resolution plots shows how much detail is lost by excessive smoothing. It is also evident that the forecast plots lose fine-scale structure due to dissipation in the model resulting mainly from horizontal diffusion. It is concluded that blobs of air on the maps at latitudes between the vortex edge and 25 deg N having potential vorticities characteristic of the vortex did indeed originate from the vortex, but that the real atmosphere is more sharply differentiated than the meteorological analyses, implying that the potential vorticity maps underestimate the amount of peeled-off material.

Tuck, A. F.↗

Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high-latitude stratosphere

The correlated set of measurements in the lower stratosphere from polar missions of the NASA ER-2 is used to derive partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. Clear evidence of the effects of heterogeneous processes in the atmosphere is found. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady-state model based on in situ NO, ClO, O3, temperature, and pressure measurements, laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs.

Kawa, S. R.↗

Ozone loss in the Arctic polar vortex inferred from high-altitude aircraft measurements

The Arctic polar vortex in winter is known to be chemically primed for ozone depletion, yet it does not exhibit the large seasonal ozone decrease that characterizes its southern counterpart. This difference may be due in part to a net flux of ozone-rich air through the Arctic vortex, which can mask ozone loss. But by using a chemically conserved tracer as a reference, significant ozone loss can be identified. This loss is found to be correlated with high levels of chlorine monoxide, suggesting that much of the decrease in ozone is caused by anthropogenic emissions of chlorofluorocarbons.

Proffitt, M. H.↗

Intercomparison of ozone measurements over Antarctica

Measurements of the abundances of ozone over Antarctica in August and September 1987 obtained during the Airborne Antarctic Ozone Experiment are intercompared. These measurements of ozone concentrations and total column abundance were obtained by three satellite instruments, two IR and one UV column-measuring instruments aboard the DC-8, one in situ DC-8, and two in situ ER-2 instruments, an upward looking lidar aboard the DC-8, and ozone sondes from four sites in Antarctica. This paper presents a summary of the ozone data, using the data and accuracies given by the individual investigators in the individual papers in this issue, without any attempt to critically review or evaluate the data. In general, very good agreement (within about 10-20 percent, limited by natural variability) among the various techniques was found, with no systematic biases detected. These observations confirm the low ozone amounts reported in the Antarctic stratosphere.

Margitan, J. J.↗

The planning and execution of ER-2 and DC-8 aircraft flights over Antarctica, August and September 1987

The significant ozone loss in the lower stratosphere over Antarctica during recent austral springs was studied by instrumented ER-2 and DC-8 aircraft. Data on the homogeneous gas composition, polar stratospheric clouds, and on tracers for dynamic motion are provided. The mission design is described, the aircraft and their payloads are documented, and the flight tracks are specified.

Tuck, A. F.↗

A chemical definition of the boundary of the Antarctic ozone hole

A program designed to study the Antarctic ozone hole using ER-2 high-altitude and DC-8 aircraft was conducted out of Punta Arenas, Chile during August 17-September 22, 1987. Graphs are presented of ozone and chlorine monoxide when crossing the boundary of the chemically perturbed region on August 23 and on September 21. Interpretations of ClO, H2O, and N2O measurements are presented, indicating ongoing diabetic cooling and advective poleward transport across the boundary.

Proffitt, M. H.↗

Causes and effects of a hole

Preliminary results from the U.S. National Ozone Expedition (NOZE) to Antarctica are reviewed. The NOZE ozonesonde measurements showed significant vertical structure in the hole, with 80 percent depletion in some of the 1 km layers but only 20 percent in adjacent layers. The depletion was confined to the 12-20 km region, beginning first at higher altitude and progressing downward. This is strong evidence against the theory that the ozone hole is due to solar activity producing odd nitrogen at high altitudes which is transported downwards, leading to enhanced odd-nitrogen catalytic cycles that destroy ozone. Nitrous oxide data show unusually low concentrations within the polar vortex, which is evidence against the theory that the hole is caused by a purely dynamical mechanism in which rising air motions within the polar vortex lead to reduced column densities of ozone. It is tentatively concluded that a chemical mechanism involving man-made chlorofluorocarbons is the likely cause of ozone depletion in the hole.

Margitan, J. J.↗

Kinetics and photochemistry Golden, D. M.

The data for chemical kinetics rate constants and photochemical cross sections taken from a compilation prepared in early 1985, entitled Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, is presented.

Demore, W. B.↗

Mechanism of the atmospheric oxidation of sulfur dioxide - Catalysis by hydroxyl radicals

A flash photolysis/resonance fluorescence technique was used to investigate the decay of OH due to the reaction OH + SO2 (+M) to HOSO2 (+M). In the presence of small amounts of NO (10 to the 14th per cu cm), the decays deviated from the normal semilogarithmic linearity due to reformation of OH. On the basis of computer simulations of the decay curves, it is suggested that the reactions HOSO2 + O2 to HO2 + SO3 (k3), and HO2 + HO to OH + NO2 are the likely subsequent steps in SO2 oxidation. The upper limit for the binding energy of HOSO2 relative to OH + SO2 is estimated to be 32 kcal/mol. The atmospheric implications of a catalytic oxidation mechanism are briefly discussed.

Margitan, J. J.↗

Kinetics of the reaction O + ClO yields Cl + O2

The kinetics of the reaction O + ClO yields Cl + O2 (k1) were studied by using resonance fluorescence to monitor the decay of O atoms which had been generated from the laser photolysis of ClO. A discharge flow system was used to generate the ClO and its concentration was measured directly by multipass absorption spectrometry. The results are k1(298) = (4.2 + or -0.8) x 10 to the -11th cu cm/s (including systematic errors) with E/R determined to lie in the range + or - 200 K. The literature data are reviewed and a composite value of k1(T) = 6.0 x 10 to the -11th exp-(100/T) is recommended for stratospheric modeling calculations. The atmospheric implications of the revised rate constant are discussed briefly.

Margitan, J. J.↗

Pressure and temperature dependence of the reaction NO2 + NO3 + M yields N2O5 + M

The pressure and temperature dependences of the reaction NO2 + NO3 + M which yields N2O5 + M are investigated by using the flash photolysis/visible absorption technique in which the pseudo-first-order decay of NO3 is monitored as a function of total pressure (20-700 torr), diluent gas (M = He and N2), and temperature (236-358 K). The reaction is found to be in the falloff region in the 20-700 torr pressure range with collision efficiencies increasing in the order He less than N2. Falloff parameters are obtained by fitting the experimental data to the falloff equation of Troe and co-workers. The expression for k1(N2 concentration, T) is obtained and compared with the evaluations presented in the NASA (DeMore, 1983) and CODATA (Baulch et al., 1982) reviews of kinetic data for atmospheric chemistry. Both evaluations are based on N2O5 thermal decomposition data coupled with estimates of the equilibrium constant. The significance of the reactions for atmospheric chemistry rests not only on their rates but on the extent to which they result in a permanent sink for NOX.

Kircher, C. C.↗

Chlorine nitrate - The sole product of the ClO + NO2 + M recombination

A laser operating at 266 nm is used to photolyze the product of the ClO + NO2 + M reaction, and the yield of Cl atoms, measured by resonance fluorescence, is found to be identical with that from equivalent concentrations of ClONO2. This is interpreted as a strong indication that no other isomers are formed in the recombination reaction. Evidence for isomers is surveyed, and the apparent forward-and-reverse-rate constant discrepancy is explained as a probable uncertainty in the thermochemistry.

Margitan, J. J.↗

Kinetics of the reaction of hydroxyl radicals with nitric acid

An extensive study was made of the reaction of hydroxyl radicals with nitric acid in a laser photolysis-resonance fluorescence system. A 266 nm laser was used to photolyze HNO3 in the temperature range 225-415 K at pressures of 20-300 torr. A temperature dependence was detected below room temperature, with a leveling off at 298 K and a wide spread in the rate constants. A pressure dependence was observed over the entire range and was more pronounced at lower temperatures. The results are noted to be in agreement with those of previous investigations. However, the wide range of rate constants are suggested to be a problem for stratospheric HO(x) modeling for anthropogenic effects. No explanation could be given of the varying results obtained by other investigators regarding the kinetics of the reactions.

Margitan, J. J.↗

Stratospheric free chlorine measured by balloon-borne in situ resonance fluorescence

Eight balloon-borne in situ measurements of ClO in the stratosphere are analyzed and are compared with recent model calculations. While the use of in situ stratospheric studies of free radicals to test models by comparing observed and predicted concentration profiles is essential for a prognosis of changes in stratospheric ozone, resulting from future changes in stratospheric ozone, such studies provide only limited insight into the nature of stratospheric photochemistry, because natural variability and the large number of fast reactions which compete in the coupling among the key radicals frustrate a detailed comparison between a mean distribution provided by the models and an instantaneous distribution provided by a single observation.

Anderson, J. G.↗