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We compare measurements of six species taken aboard NASA DC-8 and ER-2 aircraft during two flight legs in the tropical middle troposphere near Hawaii. NO, NOy, O3, CH4, and N2O measurements agree to within the limits set by the known systematic errors. For CO2, which can be measured with better relative precision than the other five species, differences in measured values from the two platforms are slightly larger than expected if the air masses sampled by the two aircraft were indeed similar in CO2 composition to better than 0.08%.

We report the first measurements of CO, CH4, N2O, CO2, and H2O(g) in the exhaust trails of T-39, B-757, and DC-8 aircraft at cruise conditions. Emission indices (EI) derived from these in-situ measurements are presented. Results are in agreement with ground-based tests indicating aircraft act as a net sink for CH4 and recent airborne in-situ measurements that N2O is not an important exhaust constituent. Condensation of H2O(g) on exhaust particles resulted in EI(H2O(g)) values less than those expected from the combustion of fuel alone. Observed apparent negative EI(H2O(g)) values suggest that aircraft aerosol emissions, under unique atmospheric conditions, seed cloud formation and lead to dehydration of the exhaust-influenced air parcel. Such conditions may induce the formation of cirrus clouds from persistent contrails. Comparisons with the Boeing EMIT Code show measurement-derived CO emission index values consistent with model evaluations.

A model of ice crystal nucleation and growth in a diluting aircraft exhaust plume is used to evaluate the physical processes responsible for the ice number densities and size distributions measured on May 4, 1996. Predicted ice crystal size distributions are compared with observations at about 70 seconds plume age. The simulated crystals grow to about 2 µm radius within 2–3 seconds, then remain approximately constant in size until 30–60 seconds plume age when crystal sublimations begins. The calculated crystal size distribution has approximately the same volume mode radius as the observed size distribution (1–2 µm); however, the model does not predict as many crystals larger than 2 µm radius as indicated by the measurements. Due to the low ambient temperature (−61°C), large ice supersaturations are generated in the plume, and all exhaust soot particles and ambient aerosols entrained into the plume before about 1 second plume age are activated to ice nuclei. The simulations indicate that if the soot particle emission index is on the order of 2×1012 particles (kg fuel)−1 or lower and freshly nucleated sulfate aerosols are too small to freeze in the young plume, then the majority of the contrail ice crystals may be nucleated on ambient aerosols entrained into the exhaust plume.

We have compared in situ measurements near the leading-edges of wave-clouds observed during the SUCCESS experiment with numerical simulations. Observations of high supersaturations with respect to ice (>50%) near the leading edge of a very cold wave cloud (T

On two days during SUCCESS, the NASA DC-8 flew carefully designed flight tracks to sample wave clouds downstream of the Rocky mountains. Wave morphology was deduced by applying linear perturbation theory to in-situ measurements of the Meteorological Measurement System (MMS) and remotely sensed isentrope profiles of the Micro-wave Temperature Profiler (MTP). Vertical winds from the MMS were consistent with updraft velocities derived from air parcel displacements estimated from the MTP. Derived wave characteristics and cooling rates are useful inputs to cloud microphysics models.

The instrumentation of a new MMS on the NASA DC-8 aircraft is briefly described. A method to compute the turbulent dissipation rate, e, is discussed in light of some apparent inconsistencies between high and medium altitude aircraft data and available theory. Examples of turbulence measurements during encounters of a wake vortex, a field of wave clouds, and persistent contrails are illustrated.

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- I I mixing ratios greater than 150 ppt. For stratospheric air parcels with CFC-11 mixing ratios less than 50 ppt (mean age greater than or equal to 5 years) we calculate inorganic bromine mixing ratios that are approximately 20% less than the photo-chemical, 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.

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 tracer's 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.

Simultaneous in situ measurements of HCl and ClO have been made for the first time in the southern hemisphere, allowing a systematic study of the processes governing chlorine activation between 15 and 20 km in the 1994 Antarctic winter. Data for several other gases (O_3, NO, NO_y, OH, HO_2, N_(2)O, CH_4, CO, H_(2)O, CFCs), particulates, and meteorological parameters were collected from the ER-2 aircraft out of New Zealand as part of the 1994 Airborne Southern Hemisphere Ozone Experiment/Measurements of Atmospheric Effects of Stratospheric Aircraft (ASHOE/MAESA) campaign. Observations from the ER-2 in the fall (April–May), prior to polar night, show that chlorine activation begins with 60–75% of inorganic chlorine as HCl. By midwinter (July–August), near-total removal of HCl is observed. The wintertime loss of HCl in air recently exposed to extreme temperatures is found to be correlated with high levels of reactive chlorine (ClO and its dimer, Cl_(2)O_2) in the linear fashion expected from the stoichiometry of the heterogeneous reaction of hydrochloric acid with chlorine nitrate on polar stratospheric clouds (PSCs): HCl + ClONO_2 → Cl_2 + HNO_3. To constrain the role of different heterogeneous reactions and PSC types, we have used a photochemical trajectory model which includes heterogeneous sulfate and PSC chemistry. Model calculations of the evolution of reactive gases are compared with the in situ observations. In addition, simultaneous measurements of OH and HO_2 are used as a diagnostic for the occurrence of the heterogeneous reaction HOCl + HCl → Cl_2 + H_(2)O, which contributes to suppressed levels of HO_x inside the vortex. It is shown that the amount of chlorine activation is not strongly dependent on the composition of PSCs. However, HO_x levels exhibit different signatures depending on the type of heterogeneous surfaces that affected chlorine activation. Furthermore, this analysis implies that in the edge region of the Antarctic vortex, the observed near-total removal of HCl can result from latitudinal excursions of air parcels in and out of sunlight during the winter, which photochemically resupply HOCl and ClONO_2 as oxidation partners for HCl.

Airborne measurements of total reactive nitrogen (NOy) and polar stratospheric cloud (PSC) aerosol particles were made in the Antarctic (68°S) as part of the NASA Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAES A) campaign in late July 1994. As found in both polar regions during previous studies, substantial PSC aerosol volume containing NOy was observed at temperatures above the frost point, confirming the presence of particles other than water ice. The composition of the aerosol particles is evaluated using equilibrium expressions for nitric acid trihydrate (NAT), nitric acid dihydrate (NAD), and the supercooled ternary solution (STS) composed of nitric acid (HNO3), sulfuric acid (H2SO4), and water (H2O). The equilibrium abundance of condensed HNO3 is calculated for each phase and compared to estimates made using observations of aerosol volume and NOy. The best agreement is found for STS composition, using criteria related to the onset and abundance of aerosol volume along the flight track. Throughout the PSC region, a comparison of the number of particles between 0.4 and 4.0 μm diameter with the number of available nuclei indicates that a significant fraction of the background aerosol number participates in PSC growth. Modeled STS size distributions at temperatures below 191 K compare favorably with measured size distributions of PSC aerosol. Calculations of the heterogeneous loss of chlorine nitrate (ClONO2) show that the reactivity of the observed PSC surface area is 30 to 300% greater with STS than with NAT composition for temperatures less than 195 K. The total volume of STS PSCs is shown to be more sensitive than NAT to increases in H2O, HNO3, and H2SO4 from supersonic aircraft fleet emissions. Using the current observations and perturbations predicted by the current aircraft assessments, an increase of 50 to 260% in STS aerosol volume is expected at the lowest observed temperatures (190 to 192 K), along with an extension of significant PSC activity to regions ∼0.7 K higher in temperature. These results improve our understanding of PSC aerosol formation in polar regions while strengthening the requirement to include STS aerosols in studies of polar ozone loss and the effects of aircraft emissions.

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.

The tracer species nitrous oxide, N2O, and the reactive nitrogen reservoir, NOy, were measured in situ using instrumentation carried aboard the NASA ER-2 high altitude aircraft as part of the NASA Airborne Southern Hemisphere Ozone Expedition/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA) and Stratospheric Tracers of Atmospheric Transport (STRAT) missions. Measurements were made throughout the latitude range of 70°S to 60°N over the time period of March to October 1994 and October 1995 to January 1996, which includes the period when the Antarctic polar vortex is most intense. The correlation plots of NOy with N2O reveal compact, near-linear curves throughout data obtained in the lower stratosphere (50 mbar to 200 mbar). The average slope of the correlation, ΔNOy/ΔN2O, in the southern hemisphere (SH) exhibited a much larger seasonal variation during this time period than was observed in the northern hemisphere (NH). Between March and October in the potential temperature range of 400 K to 525 K, the correlation slope in the SH midlatitudes increased by 28%. A smaller but still positive increase in the correlation slope was observed for higher-latitude data obtained within or near the edge of the SH polar vortex. At NH midlatitudes the correlation slope did not significantly change between March and October, while between October and January the slope increased by +7%. The larger SH midlatitude increase is consistent with ongoing descent throughout the winter and spring and also suggests that denitrification, the irreversible loss of HNO3 through sedimentation of cloud particles, is not a significant term (

Measurements of nitric oxide (NO), nitrogen dioxide (NO2), and total reactive nitrogen (NOy = NO + NO2 + NO3 + HNO3 + ClONO2 + 2N2O5 + …) were made during austral fall, winter, and spring 1994 as part of the NASA Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission. Comparisons between measured NO2 values and those calculated using a steady state (SS) approximation are presented for flights at mid and high latitudes. The SS results agree with the measurements to within 8%, suggesting that the kinetic rate coefficients and calculated NO2 photolysis rate used in the SS approximation are reasonably accurate for conditions in the lower stratosphere. However, NO2 values observed in the Concorde exhaust plume were significantly less than SS values. Calculated NO2 photolysis rates showed good agreement with values inferred from solar flux measurements, indicating a strong self-consistency in our understanding of UV radiation transmission in the lower stratosphere. Model comparisons using a full diurnal, photochemical steady state model also show good agreement with the NO and NO2 measurements, suggesting that the reactions affecting the partitioning of the NOy reservoir are well understood in the lower stratosphere.

The abundance of reactive chlorine in the lower stratosphere is observed to increase sharply with exposure to temperatures below about 195 K, a temperature which is near the nitric acid trihydrate (NAT) equilibrium condensation point. Measurements from the NASA ER-2 aircraft and a model of chemistry along back trajectories are used to examine the mechanism for this apparent temperature threshold in chlorine activation. The flight of July 28, 1994, from the Airborne Southern Hemisphere Ozone Experiment/Measurement s for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA) campaign in the southern hemisphere is studied because it provides measurements in an ongoing activation episode. Isentropic back trajectories from the aircraft sampling points indicate that the sampled air was cooling at the rate of 20 to 30 K d−1 to temperatures below the NAT condensation point and had not been below the NAT condensation point prior to that for at least 10 days. Hence the observed amount of active chlorine should be kinetically limited by the recent parcel temperatures. The measurements show enhanced ClO and decreased HCl at temperatures below 195 K even in the absence of significant polar stratospheric cloud particle surface area. The model of chemistry along back trajectories, constrained by the ER-2 chemical and microphysical measurements, indicates that an initial inorganic chlorine (Cly) partitioning of approximately half HCl and half C1ONO2 is consistent with the observations. At this initial Cly, partitioning, the model using heterogeneous reactions on liquid sulfate and ternary solutions with the most recent sticking coefficient evaluations closely reproduces the latitude gradient and temperature threshold of chlorine activation observed in the data. The sudden increase in activation in the model is a result of the steep exponential temperature dependence of the sticking coefficient for HCl+ ClONO2 on liquid aqueous solutions.

During the 1993 NASA Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE), anomalously low nitric oxide (NO) was found in a distinct sunlit layer located above the mid-latitude tropopause. The presence of a significant amount of reactive nitrogen (NO_y) in the layer implies the systematic removal of NO, which is without precedent in stratospheric in situ observations. Large increases in measured chlorine monoxide (ClO) and the hydroperoxyl radical (HO_2) also were observed in the layer. Heterogeneous reaction rate constants of chlorine nitrate (ClONO_2) with hydrogen chloride (HCl) and H_2O to form nitric acid (HNO_3) on sulfate aerosol are enhanced in the NO removal layer by local increases in H_2O and aerosol surface area. The associated conversion of NO_x (= NO + NO_2) to HNO_3 is the most likely cause of the observed low NO and NO_x/NO_y values and high ClO values.

We compare volume mixing ratio profiles of N2O, CFC-11, CFC-12, CCl4, SF6, and HCl in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov. 1994. Good agreement is found between ATMOS and in situ correlations of [CFC-11], [CFC-12], and [SF6] with [N2O]. ATMOS measurements of [CCl4] are 15% high compared to ER-2 data, but agree within the systematic uncertainties. ATMOS observations of [HCl] vs [N2O] are within approximately 10% of ER-2 data for [HCl] > 1 ppbv, but exceed in situ measurements by larger fractional amounts for smaller [HCl]. ATMOS measurements of [ClONO2] agree well with values inferred from in situ observations of [ClO], [NO], and [O3]. The sum of [HCl] and [ClONO2] observed by ATMOS, supplemented by a minor contribution from [ClO] estimated with a photochemical model, is consistent with the levels of inorganic chlorine inferred from in situ measurements of chlorine source gases.

We compare volume mixing ratio profiles of N2O, O3, NO(y) H2O, CH4, and CO in the mid-latitude lower stratosphere measured by the ATMOS Fourier transform spectrometer on the ATLAS-3 Space Shuttle Mission with in situ measurements acquired from the NASA ER-2 aircraft during Nov 1994. ATMOS and ER-2 observations of [N2O] show good agreement, as do measured correlations of [O3], [NO(y)], [H2O], and [CH4] with [N2O]. Thus a consistent measure of the hydrogen (H2O, CH4) content of the lower stratosphere is provided by the two platforms. The similarity of [NO(y)] determined by detection of individual species by ATMOS and the total [NO(y)] measurement on the ER-2 provides strong corroboration for the accuracy of both techniques. A 25% discrepancy in lower stratospheric [CO] observed by ATMOS and the ER-2 remains unexplained. Otherwise, the agreement for measurements of long-lived tracers demonstrates the ability to combine ATMOS data with in situ observations for quantifying atmospheric transport.

Measured particle volumes in a type I polar stratospheric cloud near the Antarctic polar vortex during ASHOE/MAESA show that the onset of the cloud occurred near 193 K, 3 degrees colder than nitric acid trihydrate (NAT) saturation. The onset temperature, the smooth increase of volume with decreasing temperature, the inverse correlation of particle volume and enhanced NO y (HNO 3 in the particles) with temperature, and comparisons of observations with an equilibrium model of ternary droplet growth all support the notion that much of this type I PSC was ternary solution droplets. This provides confirmation of previous findings in the northern hemisphere. However, the ternary model does not fit the observations in all regions. This may be due to the presence of some solid phase growth in agreement with impactor observations.

Extensive in situ measurements of reactive nitrogen (NO y ) and ozone (O 3 ) were made in the lower stratosphere over a broad latitude range (60°N-70°S) during two different seasons (March and October) in 1994. Both NO y and O 3 mixing ratios show a strong latitude dependence, with values increasing toward the poles. The NO y /O 3 ratio reveals a high-gradient region near the tropics that is not well-represented in standard 2-D photochemical transport models. Improving the representation by changing the horizontal eddy-diffusion coefficients near the tropics has important implications for the predicted impacts of aircraft emissions on stratospheric O 3 .

The Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE) was conducted in the spring of 1993 from Moffett Field, California (NASA Ames Research Center), utilizing the NASA high-altitude ER-2 aircraft. These northern midlatitude aircraft flights showed laminae containing high ozone concentrations, traceable to the April 1993 polar vortex breakup and corroborated by laminae of other trace gases such as CFCs, CH4, N2O, and CO2. These laminae are clearly traceable as polar vortex breakup fragments using Rossby-Ertel's potential vorticity and isentropic trajectory calculations. Laminae in stratospheric ozone profiles are commonly observed in the northern hemisphere from fall to spring, and are hypothesized to originate from very low frequency transverse waves, and/or via Rossby wave breaking. On the basis of these results, the ozone laminae observed during SPADE were a result of Rossby wave breaking during the breakdown of the polar vortex. In addition, it is shown that conventional once-per-day meteorological analyses were adequate for representing the transport of this material into the lower stratosphere midlatitudes over the course of the spring vortex breakup.

Timescales for mixing of midlatitude air into the tropical lower stratosphere are deduced from observations of long-lived tracers N2O and CCl3F. Bulk mixing between tropical and midlatitude regions is assumed to be isentropic and relatively slow compared with local mixing within each region. The mean value of the mixing timescale ranges from 12 to 18 months near 20 km. There is a tendency for shorter mixing times at higher and lower altitudes, although vertical profiles of mixing cannot be definitively established by the data. A more robust quantity is given by the fraction of midlatitude air entrained into the tropical upwelling region. Implied mixing fractions exceed 50% above 22 km.

Since the eruption of Mount Pinatubo in June, 1991, measurements of particle size and concentration have intermittently been carried out from an ER-2 aircraft at altitudes of up to 21 km at midlatitudes and high latitudes in the northern hemisphere. They show the evolution and purge of the volcanic aerosol to be due to an interaction of aerosol mechanics with tropospheric-stratospheric exchange processes, transport, and mixing. During the first 5 months after the eruption the volcanic plume spread to higher latitudes in laminae and filaments, producing steep spatial gradients in the properties of the stratospheric aerosol. At the same time the concentration of newly formed particles in the plume rapidly decreased toward background values as a result of coagulation while particle size and aerosol surface area continued to increase. By December 1991, the particle number mixing ratios and aerosol surface area mixing ratios had become spatially uniform over a wide range of latitudes above 18 km. The surface area mixing ratios peaked in this region of the stratosphere at ∼35 times their background values in the winter of 1992. The corresponding condensed mass mixing ratio enhancement was by a factor of ∼200. After the winter of 1992, a gradual removal of the volcanic mass began and initially was dominated by sedimentation above 18 km. The aerosol surface area mixing ratio thus decreased by an order of magnitude over 2.5 years, and the aerosol volume, or condensed mass, mixing ratio decayed by an order of magnitude over approximately 1.7 years. Below 18 km, the purging of the Pinatubo aerosol at mid-latitudes appeared sporadic and disorderly and was strongly influenced by episodal rapid quasi-isentropic transport and dilution by tropical air of tropospheric origin having high condensation nuclei mixing ratios but low mixing ratios of aerosol surface area or condensed mass compared to the volcanic aerosol.

BrO measured from the NASA ER-2 during Airborne Arctic Stratospheric Expedition (AASE) II exhibited a mean value (for 20-minute averages) of 5.4 +/- 0.3 pptv, with a standard deviation of 3.1 pptv. Ratios of BrO to available inorganic bromine (Br(sub y)) show only slight increases in polar regions relative to midlatitudes. A comparison between observed latitudinal and diurnal variations of this same ratio and that calculated by photochemical models shows reasonable agreement in behavior, but significant discrepancies in magnitude. It is unclear whether this difference is due to errors in measurements, models or both.

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.

Measurements of the ratio OH/HO_2, NO, O_3, ClO, and BrO were obtained at altitudes from 15–20 km and latitudes from 15–60°N. A method is presented for interpreting these simultaneous in situ observations that constrains the rates of chemical transformations that 1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO_2 and 2) control the abundance of HO_2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO_2 is complete and accurate and that the potential effects of “missing chemistry” are strictly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO_2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd nitrogen in the lower stratosphere.

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 C10 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 NO 2, suggesting a new source of HOx that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).

The response of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO2] and [O3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO2], consistent with formation and photolysis of [ClONO2]. A factor of ten range in the concentration of NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cc), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1%

The poleward transport of tropical air in the lower stratosphere during the winter period of the second Airborne Arctic Stratospheric Expedition (AASE 2) (December 1991-March 1992) is examined using contour advection calcutions. These calculations show that filaments of tropical air extend into mid-latitudes, and are wrapped around the equatorward edge of the polar jet. Simultaneously filaments are drawn from the polar vortex and are intermingled with the filaments of tropical air. The tropical filaments are consistent with measurements of chemical tracers taken aboard the ER-2 and DC-8 aircraft which show localized regions, in mid-latitudes, of air with the characteristics of tropical air.

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.

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.

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.

Measurements of stratospheric and upper tropospheric cloud water plus water vapor (total water) and water vapor were made with two Lyman alpha hygrometers as part of the STEP tropical experiment. The in situ measurements were made in the Darwin, Australia, area in January and February of 1987 on an ER-2 aircraft. Average stratospheric water vapor at a potential temperature of 375 K (the average value of Theta at the tropopause) was 2.4 parts per million by volume (ppmv). This water mixing ratio is below the 3.0 to 4.0 ppmv necessary to be consistent with the observed upper stratospheric dryness. Saturation with respect to ice and the potential for dehydration was observed up to Theta = 402 K.

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 cyclone's entire cloud shield. 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 hrs. These cells correspond to regions of enhanced convection, higher cloud altitude, and upwardly displaced potential temperature surfaces. 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 hrs, and a size comparable to the cells of low brightness temperature.

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.

In situ measurements of ClO in the winter lower stratosphere are presented for six flights of the NASA ER-2 aircraft from 38 deg N to 61 deg N. Enhanced abundances, increasing in severity with date, were observed below 20 km, where HCl and ClONO2 dominate the inorganic chlorine budget. The greatest mixing ratios, over 150 pptv, were encountered on February 20 and 21, 1989, as the vortex experienced a major warming. Although the timing of these ClO enhancements and the evidence that vortex air can reach midlatitudes suggest that heterogeneous conversion of chlorine compounds within the vortex influences chemistry at midlatitudes, the enhacements observed early in the winter could have been caused by unknown chemistry occurring outside the vortex. In either case, photochemical loss of ozone due to catalytic reactions involving ClO at these mixing ratios may be responsible in part for the ozone decreases observed at high latitudes in the Northern Hemisphere.

Mixing ratios of BrO have been measured in the Arctic lower statosphere with an instrument mounted on the NASA ER-2 aircraft. Observations from fourteen flights above the Arctic Circle in January and February of 1989 defined mixing ratios within the vortex of 4 + or - 2 parts per trillion by volume (pptv) at a potential temperature of 400 K, rising to 8 + or - 2 pptv at 470 K. These values are twice as large as values found at equivalent potential temperatures at lower latitudes, and are comparable to the mixing ratios found inside the antarctic polar vortex. Within the statistical uncertainty of the measurements, no BrO was observed in darkness at any time either inside or outside of the vortex, indicating that active bromine was sequestered in long-lived reservoirs, probably BrONO2 and BrCl. These measurements, in conjuction with measurements of ClO, demonstrate that the interaction of bromine and chlorine could represent a major sink for ozone in the presence of sunlight.

Large abundances of ClO were observed inside the Arctic polar vortex during 14 flights of the NASA ER-2 aircraft from Stavanger, Norway (59 deg N, 6 deg E) to 80 deg N latitude. Flights were conducted at altitudes between 14 and 20 km when the solar zenith angle was between 79 and 101 deg. Data are reported for three flights that represent the main features observed during the mission. These data, comparable to those obtained in the Antarctic ozone hole, indicate that the springtime Arctic polar vortex was extensively perturbed by heterogeneous chemistry and contained enough ClO to catalytically destroy ozone rapidly.

In-situ particle measurements made aboard the NASA ER-2 in the Arctic on 890130 (YYMMDD) show Type 1 PSC particles over much of the flight, with instances of embedded Type 2 PSCs. The Type 2 particles were observed at temperatures warmer than the local frost-point temperature of water; extended up to the upper size cutoff of the instrument (about 24-micron diameter); and are shown to contain too large a volume to be primarily NAT. Based on measured vertical temperature profiles, it is concluded that the Type 2 particles observed on this day were formed above the aircraft in a region where saturation with respect to ice was achieved and were sufficiently large to have fallen into the path of the ER-2. Although the amount of material in the particles, expressed as water, is small by comparison to the total (vapor + aerosol) water concentration, the flux of water from the falling particles is of sufficient magnitude, if sustained, to lead to dehydration of the source region. These observations verify the mechanism for dehydration of polar vortex air masses by precipitation of ice particles.

The ER-2 Condensation Nucleus Counter (ER-2 CNC) was operated in the Airborne Arctic Stratospheric Expedition (AASE) in January and February 1989. The ER-2 CNC measures the mixing ratio of particles, CN, with diameters from approximately 0.02 to approximately 1 micron. The spatial distribution of CN in the Arctic polar vortex was found to resemble that measured in the Antarctic in the Spring of 1987. The vertical profile of CN in the vortex was lowered by subsidence. At altitudes above the minimum in the CN mixing ratio profile, CN mixing ratios correlated negatively with that of N2O, demonstrating new particle production. CN serve as nuclei in the formation of Polar Stratospheric Clouds (PSCs) and the concentration of CN can affect PSC properties.

The ER-2 Meteorological Measurement System provides accurate in situ measurements of atmospheric state variables. During the Airborne Arctic Stratospheric Expedition (AASE) the ER-2 flew over the polar region on 14 occasions in January and February, 1989. Vertical temperature profiles, during aircraft takeoff at about 60 deg N and during midflight descent and ascent at high latitudes, are presented. Latitudinal variations of the horizontal wind measurement are illustrated and discussed. Based on observation data, model atmospheres at 60 deg and 75 deg N, representative of the environment of the AASE campaign, are developed.

This paper reports N2O measurements obtained by the Airborne Tunable Laser Absorption Spectrometer from 14 flights of the NASA ER-2 aircraft during the 1989 Airborne Arctic Stratospheric Expedition field campaign. In the altitude range expected for ozone loss, N2O has a long photochemical lifetime, making it an excellent tracer of lower stratospheric air motions. As in the southern hemisphere, the zonal wind speed maximum and large gradients of potential vorticity and N2O identify the vortex edge. The N2O profiles inside the vortex indicate net descent relative to outside the vortex and to the summer polar lower stratosphere. The descent of the N2O profile during the Arctic night relative to the summer profile is comparable to the downward shift in the vertical profile observed in the 1987 Antarctic winter vortex. Winter profiles at the poles are very similar above the 435 K potential temperature surface, but divergent below.

Particle-size distributions measured from the NASA ER-2 with the new Forward Scattering Spectrometer Probe 300 in a type I polar stratospheric cloud (PSC) on January 24, 1989 show a volume mode near 0.8 micron in diameter. The large increase in particle concentration and volume after cloud entry did not occur until the apparent saturation ratio of nitric acid with respect to nitric acid trihydrate reached 10, but at ratios near 1 subtle changes in the size distribution suggest some type I particles were present. Particle concentrations in cloud of 15-17/cu cm were greater than the CN concentrations of 5-7/cu cm just outside of cloud, suggesting nucleation on more than just sulfate particles. Some particles greater than 4 microns in diameter were observed in a region which was saturated with respect to ice.

Composite distributions of measured total reactive nitrogen NO(y), from the NASA ER-2 during the Airborne Arctic Stratospheric Expedition are presented. The observed features of these distributions are discussed in terms of the controlling dynamical, chemical and microphysical processes. In the latitudinal profile from 58 deg N to within about 4 deg poleward of the polar vortex boundary, NO(y) conforms closely to predictions of NO(y) based on N2O measurements. Poleward of 5 deg of latitude within the boundary, the average NO(y) decreases sharply and is significantly lower than that predicted from N2O. This feature is consistent with loss of NO(y) through sedimentation of particles containing NO(y) in polar stratospheric clouds.

Measurements of NO from five flights of the NASA ER-2 aircraft during the Airborne Arctic Stratospheric Expedition are presented. The NO values and vertical gradient near 60 deg N latitude are similar to previous measurements near 50 deg N in winter (Ridley et al., 1984, 1987). The NO latitudinal gradient is distinctly negative outside of the polar vortex, approaching zero at the boundary of the vortex, and remaining below the 20 pptv detection limit inside the vortex. Steady state NO2 and NO(x) (NO + NO2) are calculated from measured NO, O3, and ClO, and modeled photodissociation rates. NO(x) outside the vortex shows a negative dependence on latitude and solar zenith angle. Low NO(x) and NO(x)/NO(y), inside and near the vortex boundary may be indications of heterogeneous removal of ClONO2 and N2O5.

Calculations of ozone depletion during the 1988/89 Arctic winter using a Lagrangian coupled photochemical-microphysical model are presented. Abundances of ClO in excess of 1 ppbv were observed at the end of the Airborne Arctic Stratospheric Expedition on February 10, 1989. These are shown to be consistent with the removal of more than 90 percent of the reactive nitrogen and the conversion of more than 80 percent of reservoir chlorine to active forms. This chemical state implies that ozone losses of more than 20 ppbv/day can be sustained in heavily denitrified air throughout much of February according to current photochemistry. As much as 74 percent of the loss is calculated to be due to ClO dimer photolysis. Following the warming of the vortex in mid-February 1989, ozone loss through ClO dimer photolysis becomes less effective as the rate of thermal decomposition of the ClO dimer increases. Thus, model results suggest that thermal decomposition of the dimer plays an important role in limiting ozone loss in the Arctic spring.

Instrumentation on the NASA ER-2 high-altitude aircraft has been used to observe engine exhaust from the same aircraft while operating in the lower stratosphere. Encounters with the exhaust plume occurred approximately 10 min after emission with spatial scales near 2 km and durations of up to 10 s. Measurements include total reactive nitrogen, NO(y), the component species NO and NO2, CO2, H2O, CO, N2O, condensation nuclei, and meteorological parameters. The integrated amounts of CO2 and H2O during the encounters are consistent with the stoichiometry of fuel combustion (1:1 molar). Emission indices (EI) for NO(x) (= NO + NO2), CO, and N2O are calculated using simultaneous measurements of CO2. EI values for NO(x) near 4 g/(kg fuel) are in good agreement with values scaled from limited ground-based tests of the ER-2 engine. Non-NO(x) species comprise less than about 20% of emitted reactive nitrogen, consistent with model evaluations. In addition to demonstrating the feasibility of aircraft plume detection, these results increase confidence in the projection of emissions from current and proposed supersonic aircraft fleets and hence in the assessment of potential long-term changes in the atmosphere.

We present an analysis of the mechanisms controlling stratospheric water vapor based on in situ profiles made at 37.4°N and at altitudes up to 20 km. The stratosphere can be conveniently divided into two air masses : the overworld (potential temperature θ>380 K) and the lowermost stratosphere (θ

The paper uses particle size and volume measurements obtained with the forward scattering spectrometer probe model 300 during January and February 1989 in the Airborne Arctic Stratospheric Experiment to investigate processes important in the formation and growth of polar stratospheric cloud (PSC) particles. It is suggested on the basis of comparisons of the observations with expected sulfuric acid droplet deliquescence that in the Arctic a major fraction of the sulfuric acid droplets remain liquid until temperatures at least as low as 193 K. It is proposed that homogeneous freezing of the sulfuric acid droplets might occur near 190 K and might play a role in the formation of PSCs.

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.

In situ aircraft measurements in the lower stratosphere are used to investigate the reactive nitrogen, NO(y), total water, and particle components of the polar stratospheric cloud (PSC) aerosol in the Arctic. The results are compared to findings from the Antarctic derived using similar measurements and interpretive techniques. The Arctic data show that particle volume well above background values is present at temperatures above the frostpoint, confirming the result from the Antarctic that the observed PSCs are not water ice particles. NO(y) measurements inside a PSC are enhanced above ambient values consistent with anisokinetic sampling of particles containing NO(y). In the Arctic data over long segments of several flights, calculations show saturation with respect to nitric acid trihydrate without significant PSC particle growth above background.