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Atmosphere Research Satellite observations indicate that extensive denitrification without significant dehydration currently occurs only in the Antarctic during mid to late June.

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCI, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approximately 17-47 km) altitude range and over 10 degree latitude bins from 70 deg S to 70 deg N. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and CIONO2; (2) from the N2O-NOy correlation, (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approximately 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Recovery from enhanced chlorine conditions in the lower stratospheric polar regions of both hemispheres is investigated using data from the Upper Atmosphere Research Satellite (UARS). Microwave Limb Sounder (MLS) measurements of ClO within the polar vortices are used to infer ClO(sub x) (ClO + 2Cl202) abundances that are then correlated with simultaneous Cryogenic Limb Array Etalon Spectrometer (CLAES) measurements of ClON02 and Halogen Occultation Experiment (HALOE) measurements of HCl obtained starting within 5 days of the end of the MLS and CLAES high-latitude observing periods in each hemisphere. Time series of vortex-averaged mixing ratios are calculated on two potential temperature surfaces (585 K and 465 K) in the lower stratosphere for approximately month-long intervals during late winter: August 17 - September 17, 1992, in the southern hemisphere and February 12 - March 16, 1993, in the northern hemisphere. The observed mixing ratios are adjusted for the effects of vertical transport using diabatic vertical velocities estimated from CLAES tracer data. In the northern hemisphere, the decrease in ClO, is balanced on both surfaces by an increase in ClON02- In the southern hemisphere, continuing polar stratospheric cloud activity prevents ClO from undergoing sustained decline until about September 3. In contrast to the northern hemisphere, there is no significant chemical change in vortex-averaged ClON02 at 465 K, and there is an apparent decrease in ClON02 at 585 K, even after the enhanced ClO abundances have started to recede. Results from the SLIMCAT chemical transport model initialized with UARS data and run with OH + ClO yields HCl + 02 as an 8% channel suggest that the primary recovery product in the south during this time period is not ClON02, but HCl. HALOE HCl mixing ratios are extrapolated back to the time of the MLS and CLAES data. At 585 K, the chlorine budget can be made to balance by extrapolating HCl back to a value of 0.6 parts per billion by volume (ppbv) at the beginning of the study period; at 465 K, the contribution from extrapolated HCl is not sufficient to offset the loss in ClOx, and there is a slight imbalance between the decrease in reactive chlorine and the change in chlorine reservoirs. The difficulty in closing the chlorine budget in the southern hemisphere may arise from complications caused by ongoing activation, incomplete photochemical assumptions, and/or inadequate data quality.

The simultaneous measurements of temperature, aerosol extinction, and of the radiatively active gases by several instruments onboard the Upper Atmosphere Research Satellite permits and assessment of the uncertainties in the diagnosed stratospheric heating rates and and in the resulting residual circulation.

Simultaneous observations of Polar Stratospheric Cloud aerosol extinction and HNO3 mixing ratios over Scandinavia are examined for January 9-10, 1992. Data measured by the Microwave Limb Sounder (MLS), Cryogenic Limb Array Etalon, Spectrometer (CLAES), and Improved Stratospheric and Mesospheric Sounder (ISAMA) experiments on the Upper Atmosphere Research Satellite (UARS) are examined at locations adjacent to parcel trajectory positions.

Multiwavelength observations of Antarctic and midlatitude aerosol by the Cryogenic Limb Array Etalon Spectrometer (CLAES) experiment on the Upper Atmosphere Research Satellite (UARS) are used to demonstrate a technique that identifies the location of polar stratospheric clouds. The technique discussed uses the normalized area of the triangle formed by the aerosol extinctions at 925, 1257, and 1605/cm (10.8, 8.0, and 6.2 micrometers) to derive a spectral aerosol measure M of the aerosol spectrum. Mie calculations for spherical particles and T-matrix calculations for spheriodal particles are used to generate theoretical spectral extinction curves for sulfate and polar stratospheric cloud particles. The values of the spectral aerosol measure M for the sulfate and polar stratospheric cloud particles are shown to be different. Aerosol extinction data, corresponding to temperatures between 180 and 220 K at a pressure of 46 hPa (near 21-km altitude) for 18 August 1992, are used to demonstrate the technique. Thermodynamic calculations, based upon frost-point calculations and laboratory phase-equilibrium studies of nitric acid trihydrate, are used to predict the location of nitric acid trihydrate cloud particles.

The three-dimensional evolution of stratospheric water vapor distributions observed by the Microwave Limb Sounder (MLS) during the period October 1991 - July 1992 is documented. The transport features inferred from the MLS water vapor distributions are corroborated using other dynamical fields, namely, nitrous oxide from the Cryogenic Limb Array Etalon Spectrometer instrument, analyzed winds from the U.K. Meteorological Office (UKMO), UKMO-derived potential vorticity, and the diabatic heating field. By taking a vortex-centered view and an along-track view, the authors observe in great detail the vertical and horizontal structure of the northern winter stratosphere. It is demonstrated that the water vapor distributions show clear signatures of the effects of diabatic descent through isentropic surfaces and quasi-horizontal transport along isentropic surfaces, and that the large-scale winter flow is organized by the interaction between the westerly polar vortex and the Aleutian high.

Global variability and budgets of stratospheric nitrous oxide (N2O) are studied using output from a stratospheric version of the National Center for Atmospheric Research Climate Model (CCM2). The model extends over 0-80 km, incorporating an N2O-like tracer with tropospheric source and upper-stratospheric photochemical sink, the latter parameterized using linear damping rates obtained from detailed two-dimensional model calculations. Results from the model over several seasonal cycles are compared with observations of N2O from the Cryogenic Limb Array Etalon Spectrometer (CLAES) instrument on the Upper Atmosphere Research Satellite (UARS). The model produces N2O structure and variability that is in reasonable agreement with the observations. Global budgets of stratospheric N2O are furthermore analyzed using model output, based on the transformed Eulerian-mean, zonal-mean framework. These budgets are used to quantify the importance of planetary wave constituent transport in the stratosphere, for both slow seasonal variations and fast planetary wave events. These results demonstrate that such wave fluxes act to form and sharpen the strong subtropical N2O gradients observed in satellite measurements.

This paper discusses simultaneous measurements of stratospheric ClONO2, HNO3, temperature, and aerosol extinction coefficient by the Cryogenic Limb Array Etalon Spectrometer (CLAES) on the NASA Upper Atmosphere Research Satellite (UARS), obtained over the period 9 January 1992 through 23 April 1993. The discussion concentrates on the stratosphere region near 21 km of particular interest to heterogeneously driven ozone depletion. For periods between 12 June and 1 September 1992 at latitudes poleward of about 60 deg S, when temperatures were below type I polar stratospheric cloud (PSC) formation thresholds throughout the lower stratosphere, CLAES observed high levels of PSCs coincident with highly depleted fields of both HNO3 and ClONO2. By 17 September, the incidence of PSCs had greatly diminished in the lower stratosphere, but both CLONO2 and HNO3 remained highly depleted. These observations are consistent with the removal of gaseous HNO3 through the formation of nitric acid trihydrate (NAT) particles and the removal of ClONO2 through heterogeneous reactions on the particle surfaces. They also suggest substantial denitrification of the lower Antarctic vortex through sedimentation of PSC particles. In the Northern Hemisphere winter of 1992/93 far fewer PSCs were observed in the Arctic lower-stratosphere vortex, which had shorter periods and more localized regions of cold temperatures. Both HNO3 and ClONO2 maintained much higher levels inside the Arctic vortex than seen in the Antarctic throughout the winter/spring period. Following 28 February 1993 when Arctic vortex temperatures rose above 195 K, ClONO2 was observed in large quantities (greater than 2.1 ppbv near 21 km) inside the vortex. The persistence of relatively high levels of HNO3 inside the Arctic spring vortex compared with the low levels seen in the Antarctic spring vortex suggest a much lower level of denitrification in the Arctic.

Two stratospheric warnings during February and March 1993 are described using UKMO analyses, calculated PV and diabatic heating, and N2O observed by the CLAES instrument on the UARS. The first warming affected temperatures over a larger region. while the second produced a larger region of reversed zonal winds. Tilted baroclinic zones formed in the temperature field, and the polar vortex tilted westward with height. Narrow tongues of high PV and low N2O were drawn off the polar vortex, and irreversibly mixed. Tongues of material were drawn from low latitudes into the region between the polar vortex and the anticyclone; diabatic descent was also strongest in this region. Increased N2O over a broad region near the edge of the polar vortex indicates the importance of horizontal transport. N2O decreased in the vortex, consistent with enhanced diabatic descent during the warmings.

The transport of passive tracers observed by UARS has been simulated using computed trajectories of thousands of air parcels initialized on a three-dimensional stratospheric grid. These trajectories are calculated in isentropic coordinates using horizontal winds provided by the United Kingdom Meteorological Office data assimilation system and vertical (cross-isentropic) velocities computed using a fast radiation code.

Microwave Limb Sounder observations of mid-stratospheric ozone during stratospheric warmings show tongues of high ozone drawn up from low latitudes into the developing anticyclone.

Satellite observations of ozone and chlorine monoxide in the Arctic lower stratosphere during winter 1992-1993 are compared with observations during other winters, observations of long-lived tracers and the evolution of the polar vortex. Chlorine in the lower stratospheric vortex during February 1993 was mostly in chemically reactive forms.

Microwave Limb Sounder (MLS) H2O Cryogenic Limb Array Etalon Spectrometer (CLAES) N2O and potential vorticity calculated from UK Meteorological Office data are used to study mid-stratospheric vortex processes in the northern hemisphere winter of 1991-1992. Areas of moist air (at approx. 20 hPa) and N2O-poor air (at approx. 10hPa) are well-correlated with high values of potential vorticity and there is little or no large scale mixing across the vortex edge. We find evidence for the descent of relatively dry mesospheric air to the 840 K (approx. 10 hPa) level, as well as descent of moist air from the upper stratosphere to the 655 K (approx. 20 hPa) level. A reduction in the areas of the vortex and both the moist and H2O-poor regions is observed and there is evidence of moist and N2O-poor air parcels being extruded from the vortex.

The design and the performance of the cryogenic limb array spectrometer (CLAES) aboard the NASA Upper Atmosphere Research Satellite are discussed. CLAES measures altitude profiles of temperature, pressure, O3, H2O, CH4, N2O, NO, NO2, N2O5, HNO3, ClONO2, HCl, CFC 11, CFC 12, and aerosol absorption coefficients for atmospheric layer between 10 and 60 km. Examples of atmospheric spectral emission profiles for a number of constituents are presented as well as responsivity and noise parameters.

The Cryogenic Limb Etalon Array Spectrometer (CLAES) aboard the Upper Atmosphere Research Satellite (UARS) has made global observations of stratospheric aerosol during 1992. The instrument and measurement technique are briefly discussed. Samples of CLAES aerosol observations for south-looking days through the course of the Antarctic winter showing evolution of polar stratospheric clouds (PSCs) and the Pinatubo volcanic veil are shown and discussed.

The Cryogenic Array Etalon Spectrometer (CLAES) on the NASA Upper Atmosphere Research Satellite (UARS) began viewing the stratosphere in October 1991. This paper presents preliminary retrievals of ClONO2 and HNO3 from the CLAES measurements for selected days in June, July, August, and September of 1992 for the Southern Hemisphere. The data shows that by July 10, lower stratospheric ClONO2 and HNO3 have developed high 'collar' regions surrounding the polar vortex, and low values inside the vortex. This general structure is sustained through September 17, although the ClONO2 values inside the vortex increase significantly by this date. The data suggests that substantial sequestration of gaseous HNO3 in polar stratospheric clouds occurs in the early winter Antarctic stratosphere, accompanied by the conversion of ClONO2 to reactive chlorine through heterogeneous processes on the PSCs.

Zonal mean comparisons of CH4 (for altitude regions above the 1.35 ppmv contour), of N2O (above the 210 ppbv contour), and of F12 (above the 360 pptv contour) with UARS prelaunch climatology and with recent models shows reasonable agreement, and some interesting differences in the details of equatorial uplift and descent near the winter poles, including apparent north-south differences. Prominent features such as the double peaked uplift structure in the April-May SAMS data are clearly evident in all three CLAES tracers. Contours of SAMS CH4 and N2O occur mostly at higher pressures than in the CLAES data, presumably due in part to increased tropospheric content of these gases, and/or perhaps some dynamic difference associated with the 15 years time difference between the data sets. The CLAES F12 are the first long time base global data sets. These show more tropical uplift than climatology or models. This might suggest a somewhat shorter lifetime of F12 in the stratosphere than is currently accepted.

Two stratospheric sudden warmings during February and March 1993 are described using UKMO analyses of height, wind and temperature, PV and diabatic heating calculted from these, and N2O from the CLAES instrument on the UARS.

Chemiluminescent emission from the formation of vibrationally excited OH at an altitude of approximately 85 km presents a barrier to earth-limb measurements of NIR emissions originating in the stratosphere. High-resolution measured spectra of OH airglow have not been reported, and thus it is difficult to assess its impact on moderately-high-resolution earth-limb spectroscopy capable of looking between strong OH lines. Low-resolution rocketborne spectrometer earth-limb measurements of OH airglow are mathematically inverted to recover vibrational-state populations that are used to simulate a higher resolution spectrum in the neighbourhood of 2843/cm. Implications for remote sensing HCl are presented.

The earthlimb radiance of the HCl detector array of the CLAES instrument is simulated in order to specify and optimize the free spectral range for the etalon used in this spectral region and to select sampling positions which facilitate the recovery of HCl profiles. Considerations entering into the limb radiance computation of each contributing species are discussed. Simulations are then presented for tangent heights of 15 to 5 km for daytime and nighttime conditions, and their significance for HCl retrievals is addressed. The simulation results indicate that the HCl (P2) feature should be observable in the earth limb emission spectrum, and that an etalon with an FSR of 12.6/cm optimally avoids interference from OH emission lines blended with the HCl feature by adjacent transmission peaks.