K. R. Chan

Removal of Stratospheric O3 by Radicals: In Situ Measurements of OH, HO2, NO, NO2, ClO, and BrO

Simultaneous in situ measurements of the concentrations of OH, HO2, ClO, BrO, NO, and NO2 demonstrate the predominance of odd-hydrogen and halogen free-radical catalysis in determining the rate of removal of ozone in the lower stratosphere during May 1993. A single catalytic cycle, in which the rate-limiting step is the reaction of HO2 with ozone, accounted for nearly one-half of the total O3 removal in this region of the atmosphere. Halogen-radical chemistry was responsible for approximately one-third of the photochemical removal of O3; reactions involving BrO account for one-half of this loss. Catalytic destruction by NO2, which for two decades was considered to be the predominant loss process, accounted for less than 20 percent of the O3 removal. The measurements demonstrate quantitatively the coupling that exists between the radical families. The concentrations of HO2 and ClO are inversely correlated with those of NO and NO2. The direct determination of the relative importance of the catalytic loss processes, combined with a demonstration of the reactions linking the hydrogen, halogen, and nitrogen radical concentrations, shows that in the air sampled the rate of O3 removal was inversely correlated with total NOx, loading.

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

Reactive nitrogen (NOy) and O3 were measured simultaneously from a NASA ER-2 aircraft during 1987 through 1989. These high resolution measurements cover a broad range of latitudes in the upper troposphere and lower stratosphere. The data show a striking positive correlation between NOy and O3 in the lower stratosphere at all scales sampled. The ratio NOy/O3 is nearly independent of altitude from the tropopause to above 20 km, with ratios in the stratosphere of 0.0015–0.002 in the tropics and 0.0025–0.004 elsewhere. The ratio is much more constant than either individual species, thus providing an excellent reference point for comparing limited data sets with models. Two-dimensional models reproduce general features of the vertical profile of NOy/O3 but not the gradient in the lower stratosphere between tropics and mid-latitudes. NOy and O3 are better correlated in the lower stratosphere than in the upper troposphere. The magnitude and variability of both NOy mixing ratios and NOy/O3 ratios indicate a source of NOy in the upper troposphere. The most plausible source in the tropics is lightning production of NOx. Condensation of NOy onto aerosol particles is often possible in the tropical upper troposphere and may play a role in determining the vertical distribution of NOy. In the mid-latitude upper troposphere the data suggest long-range transport of NOy. NOy mixing ratios in the tropical upper troposphere were usually between 150 and 600 pptv, enough so that upward transport can affect the NOy abundance in the tropical lower stratosphere.

Evaluation of source gas lifetimes from stratospheric observations

Simultaneous in situ measurements of the long-lived trace species N2O, CH4, 12, CFC-113, CFC-11, CCl4, CH3CCl3, H-1211, and SF6 were made in the lower stratosphere and upper troposphere on board the NASA ER-2 high-altitude aircraft during the 1994 campaign Airborne Southern Hemisphere Ozone Experiment/ Measurements for Assessing the Effects of Stratospheric Aircraft. The observed extratropical tracer abundances exhibit compact mutual correlations that show little interhemispheric difference or seasonal variability except at higher altitudes in southern hemisphere spring. The environmental impact of the measured source gases depends, among other factors, on the rate at which they release ozone-depleting chemicals in the stratosphere, that is, on their stratospheric lifetimes. We calculate the mean age of the air from the SF6 measurements and show how stratospheric lifetimes of the other species may be derived semiempirically from their observed gradients with respect to mean age at the extratropical tropopause. We also derive independent stratospheric lifetimes using the CFC-11 lifetime and the slopes of the tracers correlations with CFC-11. In both cases, we correct for the influence of tropospheric growth on stratospheric tracer gradients using the observed mean age of the air, time series of observed tropospheric abundances, and model-derived estimates of the width of the stratospheric age spectrum. Lifetime results from the two methods are consistent with each other. Our best estimates for stratospheric lifetimes are 122±24 years for N2O, 93±18 years for CH4, 87±17 years for CFC-12, 100±32 years for CFC-113, 32±6 years for CCl4, 34±7 years for CH3CCl3, and 24±6 years for H-1211. Most of these estimates are significantly smaller than currently recommended lifetimes, which are based largely on photochemical model calculations. Because the derived stratospheric lifetimes are identical to atmospheric lifetimes for most of the species considered, the shorter lifetimes would imply a faster recovery of the ozone layer following the phaseout of industrial halocarbons than currently predicted.

Particle Formation in the Upper Tropical Troposphere: A Source of Nuclei for the Stratospheric Aerosol

Atmospheric measurements and numerical calculations described here indicate that binary homogeneous nucleation of H2SO4-H2O particles occurs in the upper tropical troposphere. Particle concentrations decrease with increasing altitude above the tropical tropopause as a result of coagulation during the upward air transport produced by stratospheric circulations. During the extended periods of time that volcanic eruptions do not strongly influence stratospheric particle number concentrations, particles formed in the upper tropical troposphere provide nuclei upon which oxidized sulfur gases condense in the stratosphere. This particle source, coupled with aerosol microphysical properties and atmospheric transport, governs the number concentration of particles in the lower tropical and mid-latitude stratosphere.

Quantifying Transport Between the Tropical and Mid-Latitude Lower Stratosphere

Airborne in situ observations of molecules with a wide range of lifetimes (methane, nitrous oxide, reactive nitrogen, ozone, chlorinated halocarbons, and halon-1211), used in a tropical tracer model, show that mid-latitude air is entrained into the tropical lower stratosphere within about 13.5 months; transport is faster in the reverse direction. Because exchange with the tropics is slower than global photochemical models generally assume, ozone at mid-latitudes appears to be more sensitive to elevated levels of industrial chlorine than is currently predicted. Nevertheless, about 45 percent of air in the tropical ascent region at 21 kilometers is of mid-latitude origin, implying that emissions from supersonic aircraft could reach the middle stratosphere.

Mixing of polar vortex air into middle latitudes as revealed by tracer‐tracer scatterplots

The occurrence of mixing of polar vortex air with midlatitude air is investigated by examining the scatterplots of insitu measurements of long-lived tracers from the NASA ER-2 aircraft during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE, April, May 1993; northern hemisphere) and the Airborne Southern Hemisphere Ozone Experiment / Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA, March-October 1994; southern hemisphere) campaigns. The tracer-tracer scatterplots from SPADE form correlation curves which differ from those measured during previous aircraft campaigns (Airborne Antarctic Ozone Experiment (AAOE), Airborne Arctic Stratospheric Experiments I (AASE I) and II (AASE II)). It is argued that these anomalous linear correlation curves are mixing lines resulting from the recent mixing of polar vortex air into the middle latitude environment. Further support for this mixing scenario is provided by contour advection calculations and calculations with a simple one-dimensional strain-diffusion model. The scatterplots from the midwinter deployments of ASHOE/MAESA are consistent with those from previous midwinter measurements (i.e., no mixing lines), but the spring CO 2 :N 2 O scatterplots form altitude-dependent mixing lines which indicate that air from the vortex edge region (but not from the inner vortex) is mixing with midlatitude air during this period. These results suggest that at altitudes above about 16 km the mixing of polar vortex air into middle latitudes varies with season: in northern and southern midwinter this mixing rarely occurs, in southern spring mixing of vortex-edge air occurs, and after the vortex breakup mixing of inner vortex air occurs.

Gravity waves generated by a tropical cyclone during the STEP tropical field program: A case study

Overflights of a tropical cyclone during the Australian winter monsoon field experiment of the Stratosphere-Troposphere Exchange Project (STEP) show the presence of two mesoscale phenomena: a vertically propagating gravity wave with a horizontal wavelength of about 110 km and a feature with a horizontal scale comparable to that of the cyclones entire cloud shield (wavelength of 250 km or greater). The larger feature is fairly steady, though its physical interpretation is ambiguous. The 110-km gravity wave is transient, having maximum amplitude early in the flight and decreasing in amplitude thereafter. Its scale is comparable to that of 100-to 150-km-diameter cells of low satellite brightness temperatures within the overall cyclone cloud shield; these cells have lifetimes of 4.5 to 6 hours. Aircraft flights through the anvil show that these cells correspond to regions of enhanced convection, higher cloud altitude, and upwardly displaced potential temperature surfaces. A three-dimensional transient linear gravity wave simulation shows that the temporal and spatial distribution of meteorological variables associated with the 110-km gravity wave can be simulated by a slowly moving transient forcing at the anvil top having an amplitude of 400–600 m, a lifetime of 4.5–6 hours and a size comparable to the cells of low brightness temperature. The forcing amplitudes indicate that the zonal drag due to breaking mesoscale transient convective gravity waves is definitely important to the westerly phase of the stratopause semiannual oscillation and possibly important to the easterly phase of the quasi-biennial oscillation. There is strong evidence that some of the mesoscale gravity waves break below 20 km as well. The effect of this wave breaking on the diabatic circulation below 20 km may be comparable to that of above-cloud diabatic cooling.

Emission Measurements of the Concorde Supersonic Aircraft in the Lower Stratosphere

Emission indices of reactive gases and particles were determined from measurements in the exhaust plume of a Concorde aircraft cruising at supersonic speeds in the stratosphere. Values for NOx (sum of NO and NO2) agree well with ground-based estimates. Measurements of NOx and HOx indicate a limited role for nitric acid in the plume. The large number of submicrometer particles measured implies efficient conversion of fuel sulfur to sulfuric acid in the engine or at emission. A new fleet of supersonic aircraft with similar particle emissions would significantly increase stratospheric aerosol surface areas and may increase ozone loss above that expected for NOx emissions alone.

Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses, of up to 1 part per billion by volume (ppbv), which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 � 4 kelvin. High ClO was always accompanied by loss of HCI mixing ratios equal to �(ClO + 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 → Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.

Distribution of halon‐1211 in the upper troposphere and lower stratosphere and the 1994 total bromine budget

We report here on the details of the first, in situ, real-time measurements of H-1211 (CBrClF2) and sulfur hexafluoride (SF6) mixing ratios in the stratosphere up to 20 km. Stratospheric air was analyzed for these gases and others with a new gas Chromatograph, flown aboard a National Aeronautics and Space Administration ER-2 aircraft as part of the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission conducted in 1994. The mixing ratio of SF6, with its nearly linear increase in the troposphere, was used to estimate the mean age of stratospheric air parcels along the ER-2 flight path. Measurements of H-1211 and mean age estimates were then combined with simultaneous measurements of CFC-11 (CCl3F), measurements of brominated compounds in stratospheric whole air samples, and records of tropospheric organic bromine mixing ratios to calculate the dry mixing ratio of total bromine in the lower stratosphere and its partitioning between organic and inorganic forms. We estimate that the organic bromine-containing species were almost completely photolyzed to inorganic species in the oldest air parcels sampled. Our results for inorganic bromine are consistent with those obtained from a photochemical, steady state model for stratospheric air parcels with CFC-11 mixing ratios greater than 150 ppt. For stratospheric air parcels with CFC-11 mixing ratios less than 50 ppt (mean age ≥5 years) we calculate inorganic bromine mixing ratios that are approximately 20% less than the photochemical, steady state model. There is a 20% reduction in calculated ozone loss resulting from bromine chemistry in old air relative to some previous estimates as a result of the lower bromine levels.