Search NASA⌕ Search

Engineering topics

Fahey, D. W.

Publications and source records attributed to Fahey, D. W..

At least 55 records · Page 3

The diurnal variation of hydrogen, nitrogen, and chlorine radicals: Implications for the heterogeneous production of HNO2

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower statosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heteogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of (OH) and (HO2) coincides with the rise of (NO) from photolysis of NO2, suggesting a new source of HO(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allow for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).

Salawitch, R. J.↗

In situ measurements of the NO2/NO ratio for testing atmospheric photochemical models

Simultaneous in situ measurements of NO2, NO, O3, ClO, pressure and temperature have been made for the first time, presenting a unique opportunity to test our current understanding of the photochemistry of the lower stratospere. Data were collected from several flights of the ER-2 aircraft at mid-latitudes in May 1993 during NASA's Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE). The daytime ratio of NO2/NO remains fairly constant at 19 km with a typical value of 0.68 and standard deviation of +/- 17. The ratio observations are compared with simple steady-state calculations based on laboratory-measured reaction rates and modeled NO2 photolysis rates. At each measurement point the daytime NO2/NO with its measurements uncertainty overlap the results of steady-state caculations and associated uncertainty. Possible sources of error are examined in both model and measurements. It is shown that more accurate laboratory determinations of the NO + 03 reaction rate and of the NO2 cross-sections in the 200-220 K temperature range characteristic of the lower stratosphere would allow for a more robust test of our knowledge of NO(X) phtochemistry by reducing significant sources if uncertainties in the interpretation of statospheric measurements.

Jaegle, L.↗

The Diurnal Variation of Hydrogen, Nitrogen, and Chlorine Radicals: Implications for the Heterogeneous Production of HNO2

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N205 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and H02 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of N02, suggesting a new source of HO, that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HN02 results in an excellent simulation of the diurnal variations of [OH] and [HO2].

Salawitch, R. J.↗

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗

In Situ Measurements of the NO2/NO Ratio for Testing Atmospheric Photochemical Models

Simultaneous in situ measurements of NO2, NO, O3, ClO, pressure and temperature have been made for the first time, presenting a unique opportunity to test our current understanding of the photochemistry of the lower stratosphere. Data were collected from several flights of the ER-2 aircraft at mid-latitudes in May 1993 during NASA's Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE). The daytime ratio of NO2/NO remains fairly constant at 19 km with a typical value of 0.68 and standard deviation of +/- 0.17. The ratio observations are compared with simple steady-state calculations based on laboratory-measured reaction rates and modeled NO2 photolysis rates. At each measurement point the daytime NO2/NO with its measurement uncertainty overlap the results of steady-state calculations and associated uncertainty. However, over all the ER-2 flights examined, the model systematically overestimates the ratio by 40% on average. Possible sources of error are examined in both model and measurements. It is shown that more accurate laboratory determinations of the NO + O3 reaction rate and of the NO2 cross-sections in the 200-220 K temperature range characteristic of the lower stratosphere would allow for a more robust test of our knowledge of NO(x) photochemistry by reducing significant sources of uncertainties in the interpretation of stratospheric measurements. The present measurements are compared with earlier observations of the ratio at higher altitudes.

Jaegle, L.↗

Spread of denitrification from 1987 Antarctic and 1988-1989 Arctic stratospheric vortices

Vertical profiles of N2O and NO(y) taken by the ER-2 outside the vortex are used to construct average vertical profiles of F(NO(y)) = NO(y)/(A-N2O), where A is the tropospheric content of N2O three years prior to the measurements. The southern hemisphere had less nitrous oxide in the range 400 less than Theta less than 470 K, by up to 25% relative to the northern hemisphere. F(NO(y)) is the ratio of NOy produced to N2O lost in a stratospheric air mass since entry from the troposphere. The profiles of F(NO(y)) have the following characteristics: (1) Relative to 1991-1992, a year without denitrification inside or outside the vortex, the northern hemisphere in 1988-1989 showed denitrification outside the vortex ranging up to 25% and averaging 17% above Theta = 425 K. (2) Relative to the northern hemisphere in 1991-1992, the southern hemisphere in 1987 showed denitrification outside the vortex ranging up to 32% and averaging 20% above Theta = 400 K. (3) Below Theta = 400 K the southern hemisphere showed enhancements of F(NO(y)) relative to the northern hemisphere in 1991-1992 ranging up to 200% at Theta = 375 K, outside the vortex. Corresponding profiles of residual water, R(H2O) = H2O - 2(1.6 - CH4), are considered and shown to be consistent with those of F(NO(y)) in the sense that they show deficits outside the Antarctic vortex, which was both dehydrated and denitrified, but not outside the 1988-1989 Arctic vortex, which was denitrified but not dehydrated. R(H2O) is the water content of stratospheric air with the contribution from methane oxidation subtracted. Comparison of F(NO(y)) and R(H2O) below 400 K outside the Antarctic vortex leads to the suggetion that dehydration in the Antarctic vortex occurs by the sedimentation of ice crystals large enough to fall out of the stratosphere, whereas denitrification occurs mainly on mixed nitric acid-water crystals which evaporate below the base of the vortex at Theta = 400 K but above the tropopause.

Tuck, A. F.↗

New photolysis system for NO2 measurements in the lower stratosphere

A new system for NO2 detection has been developed for use on the NASA ER-2 aircraft. The system converts NO2 to NO using UV photolysis with the NO product subsequently detected with an on-board chemiluminescence detector. The new system is compact, light weight, has high time resolution (approximately 1 s), and is significantly more efficient then some previous designs. Details of the system design and airborne performance are discussed.

Gao, R. S.↗

Interpretation of NO(x)/NO(y) observations from AASE-2 using a model of chemistry along trajectories

In situ measurements of NO and NO(y) are used to derive the ratio NO(x)/NO(y) along the flight track of the NASA ER-2 aircraft. Data are presented for two flights at midlatitudes in October 1991 during the Airborne Arctic Stratospheric Expedition-2 (AASE-2). Aerosol particle surface area was concurrently measured. The observations are compared with a photochemical model integrated along back trajectories from the aircraft flight track. Comparison of observations with the model run along trajectories and at a fixed position clearly and quantitatively demonstrates the importance of an air parcel's dynamic history in interpretation of local chemical observations. Comparison of the data with model runs under different assumptions regarding heterogeneous chemistry further reinforces the case for occurrence of the reaction of N2O5 + H2O on sulfate aerosol surfaces in the atmosphere. Finally, comparisons for which relative changes in the model and the data are not consistent caution that our ability to resolve all the observations is not yet complete.

Kawa, S. R.↗

The evolution of ClO and NO along air parcel trajectories

Back trajectory analysis of Arctic and Antarctic aircraft data reveals that high ClO concentrations are associated with predicted polar stratospheric cloud (PSCs) encounters. The ClO concentrations within the Arctic and Antarctic polar vortices vary widely but appear to be inversely related to parcel solar exposure since the last PSC interaction. These results imply that production of NO(x) from HNO3 photolysis and reaction with OH is the mechanism for the loss of chlorine radicals through the reformation of chlorine nitrate. Highly denitrified air parcels show no change in ClO with solar exposure. The recovery process is quantitatively duplicated using a model of chemistry along trajectories. Although PSC processing is the primary mechanism for producing elevated ClO amounts, back trajectories apparently unperturbed by PSC's also show slightly elevated ClO levels in 1992 compared to Arctic 1989 and Antarctic 1987 measurements presumably due to the presence of Pinatubo aerosol.

Schoeberl, M. R.↗

New observations of the NOy/N2O correlation in the lower stratosphere

During the Airborne Arctic Stratospheric Expedition 2 (AASE 2), September 1991 through March 1992, in situ measurements of reactive nitrogen (NO(y) and N20 were made in the Northern Hemisphere lower stratosphere. We present an analysis of this new data and compare it with results from similar data taken during AASE in the winter of 1989. In the Northern Hemisphere there is consistent linear correlation of N2O and NO(y) which shows no interannual variation. Cases of departure from a linear correlation are examined and classified as being due to denitrification (NO(y) loss) or sampling air from a region where the photochemical lifetime of NO(y) is decreased. The latter case was observed for the first time in the winter of 1992.

Loewenstein, M.↗

A case study of the mountain lee wave event of January 6, 1992

A mountain wave event, observed at the southern tip of Greenland on January 6, 1992, was corroborated by three experiments: the Meteorological Measurement System (MMS), the Microwave Temperature Profiler (MTP), and the Reactive Nitrogen Instrument (NO/NO(y)). Gravity wave signatures with classical phase relationship between wind and temperature were observed on both the outbound and inbound legs at different altitudes. The waves showed both vertically propagating and evanescent properties. Characteristics of the dominant wave mode are: wavelength about = 35 km; vertical displacement about = 0.8 km, and peak-to-peak vertical wind about = 6/ms. With the prevailing wind at about = 37/ms, the stratospheric temperature was reduced by 6K to 195.5 K within 8 minutes. The implication and potential impact of mountain lee waves on the formation of polar stratospheric clouds (PSC's) are discussed.

Chan, K. R.↗

New Observations of the NO(y)/N2O Correlation in the lower Stratosphere

During the Airborne Arctic Stratospheric Expedition II (AASE II), September 1991 through March 1992, in situ measurements of reactive nitrogen (NO(y)) and N2O were made in the Northern Hemisphere lower stratosphere. We present an analysis of this new data and compare it with results from similar data taken during AASE in the winter of 1989. In the Northern Hemisphere there is a consistent linear correlation of N2O and NO(y) which shows no interannual variation. Cases of departure from a linear correlation are examined and classified as being due to denitrification (NO(y) loss) or sampling air from a region where the photochemical lifetime of NO(y) is decreased. The latter case was observed for the first time in the winter of 1992.

Lowenstein, M.↗

A Case Study of the Mountain Lee Wave Event of January 6, 1992

A mountain wave event, observed at the southern tip of Greenland on January 6, 1992, was corroborated by three experiments: the Meteorological Measurement System (MMS), the Microwave Temperature Profiler (MTP), and the Reactive Nitrogen Instrument (NO/NO(y)). Gravity wave signatures with classical phase relationship between wind and temperature were observed on both the outbound and inbound legs at different altitudes. The waves showed both vertically propagating and evanescent properties. Characteristics of the dominant wave mode are: wavelength approximately equals 35 km, vertical displacement approximately equals 0.8 km, and peak-to-peak vertical wind approximately equals 6 ms-1. With the prevailing wind at approximately equals 37 m/s, the stratospheric temperature was reduced by 6 K to 195.5 K within 8 minutes. The implication and potential impact of mountain lee waves on the formation of polar stratospheric clouds (PSC's) are discussed.

Chan, K. R.↗

The seasonal evolution of reactive chlorine in the Northern Hemisphere stratosphere

In situ measurements of chlorine monoxide (ClO) at mid- and high northern latitudes are reported for the period October 1991 to February 1992. As early as mid-December and throughout the winter, significant enhancements of this ozone-destroying radical were observed within the polar vortex shortly after temperatures dropped below 195 K. Decreases in ClO observed in February were consistent with the rapid formation of chlorine nitrate (ClONO2) by recombination of ClO with nitrogen dioxide (NO2) released photochemically from nitric acid (HNO3). Outside the vortex, ClO abundances were higher than in previous years as a result of NO(x) suppression by heterogeneous reactions on sulfate aerosols enhanced by the eruption of Mount Pinatubo.

Toohey, D. W.↗

Stratospheric meteorological conditions in the Arctic polar vortex, 1991 to 1992

Stratospheric meteorological conditions during the Airborne Arctic Stratospheric Expedition II (AASE II) presented excellent observational opportunities from Bangor, Maine, because the polar vortex was located over southeastern Canada for significant periods during the 1991-1992 winter. Temperature analyses showed that nitric acid trihydrates (NAT temperatures below 195 K) should have formed over small regions in early December. The temperatures in the polar vortex warmed beyond NAT temperatures by late January (earlier than normal). Perturbed chemistry was found to be associated with these cold temperatures.

Newman, P.↗

Chemical Loss of Ozone in the Arctic Polar Vortex in the Winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.

Salawitch, R. J.↗

In situ measurements constraining the role of sulphate aerosols in mid-latitude ozone depletion

In situ measurements of stratospheric sulphate aerosol, reactive nitrogen and chlorine concentrations at middle latitudes confirm the importance of aerosol surface reactions that convert active nitrogen to a less active, reservoir form. This makes mid-latitude stratospheric ozone less vulnerable to active nitrogen and more vulnerable to chlorine species. The effect of aerosol reactions on active nitrogen depends on gas phase reaction rates, so that increases in aerosol concentration following volcanic eruptions will have only a limited effect on ozone depletion at these latitudes.

Fahey, D. W.↗

Reactive nitrogen and its correlation with ozone in the lower stratosphere and upper troposphere

High resolution in situ measurements of reactive nitrogen (NO(y)) and O3 were made in the upper troposphere and lower stratosphere at a variety of latitudes and seasons. In the lower stratosphere, NO(y) and O3 are very highly positively correlated at all times and spatial scales sampled. The ratio NO(y)/NO3 is much less variable than either species measured separately. The ratio has a much weaker gradient with altitude than the mixing ratios of O3 or NO(y). The ratio is smaller and decreases more rapidly with altitude in the tropics than at midlatitudes. In the upper troposphere NO(y) and O3 are only weakly correlated. Their ratio in the tropical upper troposphere is about 0.005-0.025 and the ratio in the midlatitude upper troposphere is about 0.004-0.010. The NO(y) in the upper troposhere is probably partly due to lightning.

Murphy, D. M.↗