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The chemical composition of the lowermost stratosphere exhibits both spatial and temporal variability depending upon the relative strength of (1) isentropic transport from the tropical tropopause layer (TTL), (2) diabatic descent from the midlatitude and northern midlatitude stratosphere followed by equatorward isentropic transport, and (3) diabatic ascent from the troposphere through convection. In situ measurements made in the lowermost stratosphere over Florida illustrate the additional impact of equatorward flow around the monsoon anticyclone. This flow carries, along with older stratospheric air, the distinct signature of deep midlatitude convection. We use simultaneous in situ measurements of water vapor (H2O), ozone (O3), total odd nitrogen (NOy), carbon dioxide (CO2), and carbon monoxide (CO) in the framework of a simple box model to quantify the composition of the air sampled in the lowermost stratosphere during the mission on the basis of tracer mixing ratios ascribed to the source regions for these transport pathways. The results show that in the summer, convection has a significant impact on the composition of air in the lowermost stratosphere, being the dominant source of water vapor up to the 380 K isentrope. The implications of these results extend from the potential for heterogeneous ozone loss resulting from the increased frequency and lifetime of cirrus near the local tropopause, to air with increased water vapor that as part of the equatorward flow associated with the North American monsoon can become part of the general circulation.

We examine inorganic chlorine (Cly) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO2]/[HCl] by approximately 55-60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cly partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO2 measurement (too low). The high precision of our simulation (+/-15% 1-sigma for [ClONO2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.

We use the first simultaneous in situ measurements of ClONO2, ClO, and HCl acquired using the NASA ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission to test whether these three compounds quantitatively account for total inorganic chlorine (Cly) in the lower stratosphere in 1997. We find (ClO + ClONO2 + HCl)/Cly = 0.92 +/- 0.10, where Cly is inferred from in situ measurements of organic chlorine source gases. These observations are consistent with our current understanding of the budget and partitioning of Cly in the lower stratosphere. We find no evidence in support of missing inorganic chlorine species that compose a significant fraction of Cly. We apply the analysis to earlier ER-2 observations dating from 1991 to investigate possible causes of previously observed discrepancies in the inorganic chlorine budget. Using space shuttle, satellite, balloon, and aircraft measurements in combination with ER-2 data, we find that the discrepancy is unlikely to have been caused by missing chlorine species or an error in the photolysis rate of chlorine nitrate. We also find that HCl/Cly is not significantly controlled by aerosol surface area density in the lower stratosphere.

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

In situ measurements of water vapor in the stratosphere with a new instrument are reported. The instrument has been designed to observe daytime water vapor from a multiinstrument balloon gondola that simultaneously measures free radicals such as OH, HO2, and O3 in the stratosphere up to 40 km. Lyman-alpha photofragment fluorescence is used to measure water molecules in a flowing sample of ambient air. A brief description of the instrument is given, followed by the results of the first four balloon flights. The measured mixing ratio for this flight varies from 3.0-5.5 ppmv over the altitude range of 17-34 km. Adjustments in the cooling protocol for the flights of July 6, 1988, July 28, and August 25, 1989, result in a much higher signal-to-noise ratio. Profiles from these three flights are similar to, but somewhat higher, than the 1987 profile. Implications of measurements are discussed, as are the issues of short- and long-term variability of stratospheric water vapor.

Bromine monoxide was observed in situ during nine flights of the NASA ER-2 aircraft from Punta Arenas, Chile (54 deg S latitude), to 72 deg S latitude over the Palmer Peninsula, Antarctica. The first flight for the BrO detection system was on August 28. The distribution of BrO inside the chemically perturbed region defined by greatly elevated ClO abundances was different from that found just outside. Inside, the BrO mixing ratio was 6.1 + or - 1.1 pptv above the 440 K potential temperature surface, 4.7 + or - 2.0 pptv between the 400 and 440 K surfaces, and less than 4 pptv below the 400 K surface. At high latitudes outside the chemically perturbed region, the BrO mixing ratio was 5.4 + or - 1.4 pptv near the 450 K surface, but decreased to 2.9 + or - 1.2 pptv at the 420 K surface. The abundance of BrO showed no discernible temporal trend during the course of the nine flights. Away from the south polar region, at latitudes between 47 deg S and 37 deg N and potential temperatures between 435 and 500 K (18.5- to 20.7-km altitude), the BrO mixing ratio was 0.5-3.0 pptv.

A photochemical model consisting of 40 species and 107 reactions is integrated along 80-day air parcel trajectories calculated in the lower stratosphere for the springtime Antarctic. For the trajectory starting at 58 deg S, which may be regarded as outside the circumpolar vortex, only a small change in O3 occurs in the model. In contrast, for the air parcel starting in the vortex at 74 deg S, the O3 concentration is reduced by 93 percent during the 80 days from the beginning of August to late October. The model results for several species are compared with measurements from the Airborne Antarctic Ozone Experiment and, in general, good agreement is obtained. In the model, the dentrification of the air parcels in polar stratospheric clouds increases the amount of chlorine present in active form. Heterogeneous reactions maintain high active chlorine which destroys O3 via the formation of the ClO dimer. Results of calculations with reduced concentrations of inorganic chlorine show considerably reduced O3 destruction rates and compare favorably with the behavior of total O3 since the late 1970s. The remaining major uncertainties in the photochemical aspects of the Antarctic ozone hole are highlighted.

The spatial and temporal distributions of ClO in the latitude belt from 54 to 72 deg S during the later stages of austral winter were obtained from measurements aboard the ER-2 aircraft flying at the altitude of about 18 km into the Antarctic polar vortex. Mixing ratios of about 10 parts per trillion by volume (pptv) were found in the vicinity of 55 deg S, increasing to 50 pptv at 60 deg S. A steep gradient of the ClO mixing ratio occurred in the vicinity of 65 deg S, where, at a fixed potential temperature, the value of the ClO mixing ratio increased by an order of magnitude within a very few degrees of latitude, defining the edge of the 'chemically perturbed region' (CPR). At the southern extension of the flight track, peak mixing ratios increased sharply from 800 pptv on August 23 to 1100 pptv in early September, and then increased more slowly to 1200 pptv on September 22. This corresponds to enhancements 500 times the typical mid-latitude values.

The concentrations and the time development of chlorine and nitrogen trace gases in the Antarctic stratosphere before, during, and after the Airborne Antractic Ozone Experiment (AAOE) were simulated using photochemical models of the Antractic stratosphere during winter/spring. The initial conditions in the calculations were constrained using observations by the AAOE instrument. The comparison of calculated results with the AAOE measurements of HCl and ClO suggest that heterogeneous chemistry was maintained throughout the month of September 1987.

The chemical evolution of the Antarctic vortex region was studied during August 23-September 22, 1987 on the basis of in situ O3 and ClO data collected by the ER-2 aircraft. Particular attention is given to the evolution of the ClO-O3 anticorrelation from the first flight on August 23, 1987, which penetrated well into the vortex, through the course of 10 flights culminating on September 22, 1987. It is concluded that the disappearance of ozone within the Antarctic vortex results from halogen-catalyzed recombination of O3 to molecular oxygen.

Results from the Lagrangian photochemical model integrated along computed air parcel trajectories intersected by the ER-2 aircraft are presented and compared with AAOE observations. According to the model, the BrO observations made from the ER-2 within the dehydrated denitrified region are consistent with there being approximately 5 parts per trillion by volume of BrO(y) at 428 K in spring. Within the high ClO region, ozone destruction rates are expected to exceed 2 percent/d with approximately 80 percent due to the ClO dimer mechanism.

The kinetics of ozone destruction within the Antarctic polar vortex are studied via simultaneous in situ observations of ClO, BrO, O3, N2O, pressure, and temperature. It is found that the chlorine dimer mechanism rate, limited by the reaction ClO + ClO + M yields ClOOCl + M, contributes the most to the integrated rate of ozone destruction within the vortex on isentropic surfaces between altitudes of 14 and 18.3 km.

A high-sensitivity, in situ UV absorption ozone sensor has been developed for use in the stratosphere. The instrument couples 254-nm radiation from a low-pressure mercury discharge lamp into a 40-pass White cell to attain a high-sensitivity ozone absorption measurement. Preflight/postflight laboratory tests utilizing an ozone source coupled to a laboratory UV ozone photometer in a fast-flow system as well as in-flight diagnostics verify the successful operation of the instrument. Evidence is presented to verify that in situ UV absorption ozone photometers can measure stratospheric ozone with better than 3 percent precision and 5 percent accuracy, provided proper attention is given to both the thermal field surrounding the gondola and the ambient pressure measurements. Ozone data are compared with modeled profiles in the 28- to 40-km region. An assessment of the disagreement between observations and modeled profiles is given along with suggestions for future experiments designed to constrain photochemical models.

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.

A volume density profile of the OH radical throughout the 45- to 70-km region of the earth's upper atmosphere is presented. A high-resolution polarized Ebert-Fastie spectrometer flown aboard a sounding rocket was used to obtain the data. The molecule was found to have a scale height significantly greater than that of the atmosphere, with local densities of 4.4 million/cu cm at 50 km, 5.5 million/cu cm at 60 km, and 3.5 million/cu cm at 70 km.