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The OH number density in the stratosphere has been measured over the altitude interval of 37 to 23 km at midday via a balloon-borne gondola launched from Palestine, Texas on July 6, 1988. OH radicals are detected with a laser-induced fluorescence instrument employing a 17-kHz-repetition-rate copper vapor laser-pumped dye laser optically coupled to an enclosed flow, in-situ sampling chamber. OH abundances ranged from 88 + or - 3l pptv in the 36 to 35 km interval to 0.9 + or - 0.8 pptv in the 24 to 23 km interval. The stated uncertainty includes that from both measurement precision and accuracy. Simultaneous detection of ozone and water vapor densities was carried out with separate on-board instruments.

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.

Midday stratospheric OH density measurements have been carried out within the altitude interval of 31 to 24 km using the laser-induced fluorescence technique deployed on a balloon-borne gondola launched from Palestine, Texas on July 15, 1987. Laser output at 282 nm is produced with a pulsed, 17 kHz repetition rate, copper vapor laser pumped tunable dye laser. The OH mixing ratio ranged from 16 + or - 5 ppt at 31 km to 4 + or - 3 ppt in the 27 to 24 km region. Simultaneous ozone and water vapor measurements were also obtained with separate instruments.

Bromine monoxide was observed in situ at approximately 18 km altitude during nine flights of the NASA ER-2 aircraft from Punta Arenas, Chile (54 altitude) to 72 S latitude over the Palmer Peninsula, Antarctica. The first flight for the BrO detection system was on 28 August. Here, the results from the flights over Antarctica and from the ferry flights from Punta Arenas to Moffett Field, CA (37 N latitude are reported. A key question concerning BrO, then, is how it is distributed with respect to the chemical containment vessel defined by elevated ClO mixing ratios. This question is answered with greatest statistical significance if the data are averaged into five regions: outside the vessel, aircraft heading south; inside the vessel on the same potential temperature surface; in the dive region; inside the vessel on a given potential temperature surface, aircraft heading north; and outside the vessel on the same surface. The result is that the BrO distribution inside the chemical containment vessel was different from that found outside. Inside, the BrO mixing ratio was (5.0 plus or minus 1.1) pptv between the 400 K and 460 K potential temperature surfaces, decreasing only slightly with potential temperature, and was less than 3.6 pptv below the 4 00 K surface. The abundance of BrO inside the chemical containment vessel showed no discernible temporal trend during the course of the nine flights. Outside the vessel, the BrO mixing ratio was (4.7 plus or minus 1.3) pptv near the 450 K surface, but decreased to (2.8 plus or minus 1.0) pptv near the 420 K surface.

Results from a series of 12 ER-2 aircraft flights into the Antarctic polar vortex are summarized. These in situ data define the spatial and temporal distribution of ClO as the aircraft flew at an altitude of approx. 18 km from Punta Arenas (54 deg S latitude) to the base of the Palmer Peninsula (72 deg S latitude), executed a rapid descent to approx. 13 km, turned north and climbed bach to approximately 18 km, returning to Punta Arenas. A general pattern in the ClO distribution is reported: mixing ratios of approximately 10 ppt are found at altitude in the vicinity of 55 deg S increasing to 50 ppt at 60 degrees S. In the vicinity of 65 deg S latitude a steep gradient in the ClO mixing ratio is observed. At a fixed potential temperature, the ClO mixing ratio through this sharp transition increases by an order of magnitude within a very few degrees of latitude, thus defining the edge of the chemical containment vessel. From the edge of that containment vessel to the southern extension of the flights, 72 deg S, a dome of slowly increasing ClO best describes the distribution. Conclusion are drawn from the data.

Measurements of lower stratospheric ClO taken during a NASA ER-2 flight between Moffett Field, CA (37 N, 122 W) and Great Slave Lake, Canada (61 N, 116 W) on 13 February 1988 are reported. Northbound, the aircraft was flown at about 20 km altitude from 39 N to 56 N, at 18 km from there to 58 N, in a descent to 15 km at 60 N, and in a rise and turn at the northernmost point. The southbound leg was flown in a gradual climb from 20 km to 21.5 km. On this day, the central position of the Arctic polar vortex, as determined by an NMC analysis of heights and temperatures at the 50 mb and 70 mb levels, was approximately 79 N, 100 W. Because the vortex was located on the North American side of the pole, the aircraft was able to reach a point slightly inside the maximum horizontal wind region where wind speeds were 80 to 90 knots. The general pattern for the observed ClO is that it increased with both latitude and altitude, and attained a maximum of about 55 pptv at 61 N latitude and 20.5 km altitude. This value is about 20 times smaller than the maxima observed over Antarctica, but is comparable to those seen just outside the chemical containment vessel located inside the Antarctic Polar vortex. On the other hand, in a comparison with northern midlatitude data taken on this and three other February flights, ClO mixing ratios observed north of 55 N latitude are 2 to 5 times larger at all flight altitudes (15 to 20 km). Possible reasons are discussed for this enhancement over midlatitude and the evidence is considered for whether or not the instruments sampled Arctic polar vortex air. A second feature of the data is the strong positive correlation between ClO and O3 during the entire flight.

Midlatitude stratospheric ClO at altitudes below 22 km has been measured for the first time. Measurements were made at latitudes between 27 and 48 deg N during three flights from Moffett Field, CA, in June and July of 1987, with a new instrument flown on the NASA ER-2 aircraft. The result from these flights is that the ClO mixing ratio increases from less than 0.5 pptv at 16.8 km to 2.0 pptv at 18.3 km and 10.1 pptv at 21 km. These altitude profiles agree with an extrapolated profile from a May 1986 balloon-borne experiment (Brune and Anderson, 1986).

Results of the second flight of the Harvard Reel Down balloon-born winching system, in which a more complex photochemical detection package was twice lowered from a float altitude of 39 km and reeled back to the winch, are reported. Modifications over the original package design include improvements to the winch platform and reconstruction of the suspended detection package for specific ClO measurement and for tight weight control. Controlled velocities of 4-7 m/sec were implemented for both of the scans, and the package was brought to a brief stop during the first scan to evaluate dynamic effects. The results demonstrate the operational effectiveness of the system.

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.

Stratospheric chlorine monoxide concentrations were measured in situ using a new and improved observational method in which the detection package is lowered on a tether from a balloon-borne platform floating near 40 km altitude and then reeled back up. Two reel down and reel up sequences covering 38 to 31 km produced (ClO) profiles which agree with each other to + or - 12 percent. The measured (ClO) profile falls within the envelope of nine previous fast parachute drop results, but exhibits a different shape, peaking near 32 km as opposed to approximately 39 km for the average of the previous profiles. These results are lower than but consistent with the profiles derived from remote sensing methods, and indicate the need for simultaneous measurements of relevant species.

Balloon-borne winch system; stratospheric free radicals; stratospheric sounding; copper vapor lasers; ozone measurement; NO2 analysis; chlorine chemistry; trace elements; and ClO observations are discussed.

A balloon-borne winching system has been developed for extending a very long tether with payload down into the stratosphere and recovering it, this has been flight proven by being carrried to an altitude of 40 km, lowering a 62-kg stratospheric photochemistry experiment 12 km at a descent velocity of about 6-8 m/sec and recovering it at comparable velocities. During the first flight, the data gave no evidence of dynamic instabilities due to the system or the stratospheric interactions. The future utility of this payload is discussed with attention to the design factors that bound the range of performance of this type of system.

A balloon-borne winch system has been developed and flight tested which permits the repetitive lowering and hoisting of a stratospheric sampling payload for distances of up to 20 km from a float altitude of 35-40 km. This new approach to in situ stratospheric measurements permits multiple scans of various depths and velocities, closely spaced over a period of hours or days, thus dramatically increasing observational effectiveness. The motor driven winch permits control of ascent velocities from 0-9 m/s with energy derived from a large battery; for descent, the motors are used as generators, velocity is controlled over the same range, and the energy is dumped radiatively to space. The 1.75 mm diameter tether is of braided Kevlar construction with a nylon jacket; it exhibits a 2900 N break strength. Both the winch and the payload suspended by the tether are fully instrumented to evaluate potentially destructive system-induced dynamics and the effects of stratospheric wind shears. The system was successfully flight tested by lowering a 62 kg payload for a distance of 12 km from a float altitude of 38.5 km and hoisting it back up again, both at velocities ranging between 5-9 m/s. Observations indicated minimal system-induced dynamical effects, and no adverse effects due to the 8 m/s wind shear present during flight.

The letter reports two recent in-situ measurements of OH in the stratosphere between altitudes of 29 and 43 km using a resonance fluorescence technique that was previously employed for the measurement of ground-state atomic oxygen. The experimental technique is described in detail along with the photon detector and the absolute-calibration procedure. The results are found to indicate OH concentrations that approach the maximum predicted by current stratospheric photochemical theory.

The densities of O(3P) and N(4S) at 225 km were determined during the Apollo Soyuz Test Project by a resonance absorption/fluorescence technique in which OI and NI line radiation produced and collimated on board the Apollo was reflected from the Soyuz back to the Apollo for spectral analysis. The two spacecraft maneuvered so that a range of observation angles of plus or minus 15 deg with respect to the normal to the orbital velocity vector was scanned. The measurements were made at night on two consecutive orbits at spacecraft separations of 150 and 500 m. The resulting relative counting rates as function of observation angle were compared to calculated values to determine the oxygen value. This value agrees with mass spectrometric measurements made under similar conditions. The nitrogen value is in good agreement with other measurements and suggests a smaller diurnal variation than is predicted by present models.

The reaction of OH radicals with D-atoms to form OD has been studied at room temperature in a discharge-flow system utilizing UV resonance fluorescence detection of the molecular species. A rate constant of approximately 1.3 by 10 to the -10th power cu cm per sec is reported where the error limits include systematic error estimates. Astrophysical and kinetic implications are discussed briefly.

Results are presented for an experimental application of the laminar flow-through/resonance technique, which allows direct observations of the absolute concentration of atoms and radicals in the earth's upper atmosphere. Atomic resonance fluorescence was used in conjunction with a parachute-borne flow-through module deployed from a balloon at a height of 40 km to determine the concentration of ground-state atomic oxygen at 40 to 25 km in the atmosphere. The equipment is described, and the measurements and experimental uncertainties are plotted. It is shown that the observed absolute concentration of ground-state atomic oxygen is similar to that predicted by model calculations, and it is concluded that this technique provides a simple and direct means of measuring atomic and radical concentrations in the part-per-trillion range in unperturbed stratospheric samples.

The reaction OH + HN3 yields H2O + NO3 was studied over the temperature range 270-470 K in a flow system utilizing UV resonance fluorescence detection of OH. A temperature independent rate constant of (8.9 plus or minus 1.3) x 10 to the -14 cu cm/s was obtained, where the reported uncertainty represents a single standard deviation including estimates of systematic errors.

Measurements results are presented for the rate constant of the reaction OH + HCl yields H2O + Cl determined in a flow tube over the temperature range of 224 to 460 K using resonance fluorescence detection of OH. Stratospheric and reaction kinetic implications are briefly discussed.

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.

The Tethered Satellite System in combination with in situ atomic and molecular resonance fluorescence techniques can treat the problem of simultaneously determining the absolute density of atomic and molecular species known to control the photochemical structure of the upper atmosphere. Two familities of reactants which can be treated by these techniques are the nitrogen oxygen family and the hydrogen oxygen family.

The densities of O(3P) and N(4S) at 225 km were determined during the Apollo-Soyuz Test Project by a resonance absorption-fluorescence technique in which O I and N I line radiation produced and collimated on board the Apollo was reflected from the Soyuz back to the Apollo for spectral analysis. The two spacecraft maneuvered so that a range of observation angles of plus or minus 25 deg with respect to the normal to the orbital velocity vector was scanned. The measurements described were made at night on two consecutive orbits at spacecraft separations of 150 and 500 m. The results indicate an O density of 1.15 billion per cu cm (plus or minus 30%), agreeing with mass-spectrometric measurements made under similar conditions, and an N density of 5.6 to 11.2 million per cu cm, in good agreement with recent measurements but suggesting a smaller diurnal variation than predicted by present models.

A laminar flow through resonance fluorescence technique, which permits the direct measurement of absolute density for most atomic and diatomic constituents in the stratosphere was developed. This system is shown schematically and its use in determining O(3p) and OH densities is described.