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Vertical profiles of stratospheric HOCl calculated with a diurnal steady-state photochemical model that uses currently recommended reaction rates and photolysis cross sections underestimate observed profiles of HOCl obtained by two balloon-borne instruments, FIRS-2 (a far-infrared emission spectrometer) and MkIV (a mid-infrared, solar absorption spectrometer). Considerable uncertainty (a factor of two) persists in laboratory measurements of the rate constant (k(sub 1)) for the reaction ClO + HO2 yields HOCl + O2. Agreement between modeled and measured HOCl can be attained using a value of k(sub 1) from Stimpfle et al. (1979) that is about a factor-of-two faster than the currently recommended rate constant. Comparison of modeled and measured HOCl suggests that models using the currently recommended value for k(sub 1) may underestimate the role of the HOCl catalytic cycle for ozone depletion, important in the midlatitude lower stratosphere.

The HOCl catalytic cycle is an efficient ozone loss mechanism in the lower mid-latitude stratosphere. We use a diurnal steady-state photochemical model to calculate profiles of HOCl for conditions encountered by a number of high-altitude balloon flights. To assess how well this model represents ozone loss by the HOCl cycle, we compare our calculations of HOCl and its precursors Cl0 and HO2 with measurements obtained by an FTIR solar absorption spectrometer (MkIV), a far-infrared emission spectrometer (FIRS-2), and a submillimetenvave limb sounder (SLS). We then evaluate these comparisons in light of a number of recent laboratory studies of the main formation mechanism of HOCl, the reaction of Cl0 + HO2. Those studies measured both the reaction rate constant and the quantum yield for a second product pathway, formation of HCl.

The morphology and evolution of the stratospheric ozone (O3) distribution at high latitudes in the Northern Hemisphere (NH) are examined for the late summer and fall seasons of 1999. This time period sets the O3 initial condition for the SOLVE/THESEO field mission performed during winter 1999-2000. In situ and satellite data are used along with a three-dimensional model of chemistry and transport (CTM) to determine the key processes that control the distribution of O3 in the lower-to-middle stratosphere. O3 in the vortex at the beginning of the winter season is found to be nearly constant from 500 to above 800 K with a value at 3 ppmv +/- approx. 10%. Values outside the vortex are up to a factor of 2 higher and increase significantly with potential temperature. The seasonal time series of data from POAM shows that relatively low O3 mixing ratios, which characterize the vortex in late fall, are already present at high latitudes at the end of summer before the vortex circulation sets up. Analysis of the CTM output shows that the minimum O3 and increase in variance in late summer are the result of: 1) stirring of polar concentric O3 gradients by nascent wave-driven transport, and 2) an acceleration of net photochemical loss with decreasing solar illumination. The segregation of low O3 mixing ratios into the vortex as the circulation strengthens through the fall suggests a possible feedback role between O3 chemistry and the vortex formation dynamics. Trajectory calculations from O3 sample points early in the fall, however, show only a weak correlation between initial O3 mixing ratio and potential vorticity later in the season consistent with order-of-magnitude calculations for the relative importance of O3 in the fall radiative balance at high latitudes. The possible connection between O3 chemistry and the dynamics of vortex formation does suggest that these feedbacks and sensitivities need to be better understood in order to make confident predictions of the recovery of NH O3.

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Understanding stratospheric ozone loss to the point of accurately predicting ozone in the future requires correctly distinguishing chemical from transport-induced changes in ozone. For example, evaluating the impact of chlorine reduction in controlling stratospheric ozone loss requires estimating the amount of ozone lost in chemical reactions in the polar winter and spring. The Northern Hemisphere winter polar region is a particularly crucial and interesting area because it appears that the Northern vortex may currently be poised near the threshold of extreme ozone destruction such as that which now occurs annually in the Antarctic ozone "hole." In this presentation we explore the interaction of ozone transport and chemistry through the Northern late summer and fall seasons as the vortex circulation becomes established. This phase of the seasonal cycle determines the starting point for heterogeneous processes and chlorine-driven loss that take control in the winter vortex. Using a combination of profile data from POAM, HALOE, and in situ measurements, we show that relatively low ozone at high latitudes in the middle stratosphere is associated with vortex airmasses and that these ozone abundances evolve photochemically from characteristically higher values at the end of the summer. The zonal variance of ozone mixing ratio also increases greatly at this time consistent with increasing wave-driven transport. Comparison with a three-dimensional chemistry-transport model is used to generalize the findings from the limited set of observations and quantify the relative roles of transport and chemistry in determining the ozone mixing ratio distributions.

Volume mixing ratio profiles of HCl, HOCl, ClNO3, CH3Cl, CFC-12, CFC-11, CCl4, HCFC-22, and CFC-113 were measured simultaneously from 9 to 38 km by the Jet Propulsion Laboratory MkIV Fourier Transform Infrared solar absorption spectrometer during two balloon flights from Fairbanks, Alaska (64.8 N), on May 8 and July 8, 1997. The altitude variation of total organic chlorine (CCly) total inorganic chlorine (Cly), and the nearly constant value (3.7 +/- 0.2 ppbv) of their sum (Cl(sub TOT)) demonstrates that the stratospheric chlorine species available to react with O3 are supplied by the decomposition of organic chlorinated compounds whose abundances are well quantified. Measured profiles of HCl and ClNO3 agree well with profiles found by photochemical model (differences < 10% for altitudes below 35 km) constrained by various other constituents measured by MkIV. The production of HCl by ClO + OH plays a relatively small role in the partitioning of HCl and ClNO3 for the sampled air masses. However, better agreement with the measured profiles of HCl and ClNO3 is obtained when this source of HCl is included in the model. Both the measured and calculated [ClNO3]/[HCl] ratios exhibit the expected near linear variation with [O3]2/[CH4] over a broad range of altitudes. MkIV measurements of HCl, ClNO3, and CC1y agree well with ER-2 in situ observations of these quantities for directly comparable air masses. These results demonstrate good understanding of the budget of stratospheric chlorine and that the partitioning of inorganic chlorine is accurately described by photochemical models that employ JPL97 reaction rates and production of HCl from ClO + OH for the environmental conditions encountered: relatively warm temperatures, long periods of solar illumination, and relatively low aerosol surface areas.

Measurements of HCl in the lower stratosphere (15-21 km) from aircraft, balloon, Space Shuttle, and satellite reveal a growth in its mean abundance relative to that of total inorganic chlorine (Cly) from HCl/Cly = 57(+/-5)% in early 1993 to 75(+/-7)% by the end of 1997.

Volume mixing ratio profiles of the quantitatively significant NOy species NO, NO2, HNO3, HNO4, CINO3 and N2O5 were measured remotely form 8 to 38 km by the JPL MkIV FTIR solar absorption spectrometer during balloon flights from Fairbanks, Alaska on May 8 and July 8, 1997.

The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at theta approximately 330-380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12-24 ppmv) and CO2 for the admixed tropospheric air at theta = 352-364 K. Temperatures on the 355 K surface 20-40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for theta < 362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.

In situ measurements of CO were made in the upper troposphere and lower stratosphere (7 to 22 km altitude) with the JPL Aircraft Laser Infrared Absorption Spectrometer (ALIAS) on 58 flights of the NASA ER-2 aircraft from October 1995 through September 1997, between 90 degrees North and 3 degrees South latitude.

Simultaneous in situ measurements of the long-lived trace gases N(sub 2)O and CH(sub 4) were made with a tunable diode laser spectrometer (ALIAS II) aboard the Observations from the Middle Stratosphere (OMS) balloon platform from New Mexico, Alaska, and Brazil during 1996 and 1997.

Establishing a quantitative understanding of the abundance of peroxynitric acid (HNO4) is of interest because the reaction of OH with HNO4 is believed to be a significant sink for HO(x) in the lower stratosphere and upper troposphere. We present concentration profiles of KNO4 obtained by the MkIV Fourier transform infrared spectrometer using the solar occultation technique during two flights, one at 35 N on 25 September 1993 (930925) and the other near 66 N on 7 May 1997 (970507). The observations of HN04 present an apparent dilemma: the calculated profile for HNO4 found using standard kinetics is in relatively good agreement with the mid-latitude observations, but the calculated profile for HNO4 found using the same kinetics overestimates the high-latitude summer observations by nearly a factor of two. Resolution of this dilemma is the focus of our investigation. We show that introduction into our photochemical model of a speculative long-wave (lambda greater than 650 nm) photolytic pathway for HNO4 leads to good agreement between theory and observation of HN04 for both the mid-latitude and high-latitude regions. Implications for the budget of HO(x) are also discussed.

Measurements of hydrogen, nitrogen and chlorine radicals from a balloon flight on 25 September 1993 from Ft. Sumner, NM provide an opportunity to quantify photochemical production and loss of stratospheric ozone. Ozone loss rates determined using measured radical concentrations agree fairly well with loss rates calculated using a photochemical model. Catalytic cycles involving OH and HO2 are shown to dominate photochemical loss of ozone for altitudes between 44 and 50 km. Reactions involving NO and NO2 are the dominant sink for ozone between 25 and 38 km. The total ozone loss rate determined from the measurements balances calculated production rates for altitudes between 30 and 40 km. However, loss of ozone exceeds production by -35% between 42 and 50 km. The imbalance between production and loss of ozone above 42 km is larger than the uncertainty of any one of the critical kinetic parameters or species concentrations. No single adjustment to any of these parameters can simultaneously resolve the imbalance and satisfy constraints imposed by measured OH, HO2, NO2 and ClO. Our results are consistent with an additional mechanism for ozone production above 40 km other than photolysis of ground state O2.

In situ measurements of hydrochloric acid (HCI) concentrations in the lower stratosphere from 1991 to 1996 reveal that its abundance relative to that of total inorganic chlorine (CIy) has evolved upwards from HCI/CIy=40% in late 1991 to 70% in 1996.

We present volume mixing ratio profiles of NO, NO2, HNO3, HNO4, N2O5, and CINO3 and their composite budget (NOy), from 20 to 39 km, meassured remotely in solar occultation by the JPL MkIV Interferometer during a high-altitude ballon flight from Fort Sumner, New Mexico on 25 September 1993.

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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 (NOy) 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.

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.

This paper describes the validation of ozone data from the Upper Atmosphere Research Satellite (UARS) Microwave Limb Sounder (MLS). The MLS ozone retrievals are obtained from the calibrated microwave radiances (emission spectra) in two separate bands, at frequencies near 205 and 183 GHz. Analyses described here focus on the MLS Version 3 data (the first set of files made publicly available). We describe results of simulations performed to assess the quality of the retrieval algorithms, in terms of both mixing ratio and radiance closure. From actual MLS observations, the 205-GHz ozone retrievals give better closure (smaller radiance residuals) than that from the 183-GHz measurements and should be considered more accurate from the calibration aspects. However, the 183-GHz data are less noise limited in the mesosphere and can provide the most useful scientific results in that region. We compare the retrieved 205-GHz ozone profiles in the middle-to lower stratosphere to ozonesonde measurements at a wide range of latitudes and seasons. Ground-based lidar data from Table Mountain, California, provide a good reference for comparisons at higher altitudes. Based on these analyses, comparisons with balloon-borne measurements and others, as well as a detailed budget of estimated uncertainties, MLS results appear to be generally of high quality, with some biases worth mentioning. Results for the lowermost stratosphere (approx. 50 to 100 bPa) are still in need of improvement. A set of estimated precision and accuracy values is derived for the MLS ozone data sets. We also comment on recent updates in the retrieval algorithms and their impact on ozone values.

Measurements of hydrogen, nitrogen and chlorine radicals from a balloon flight on 25 September 1993 from Ft. Sumner, NM provide an opportunity to quantify photochemical production and loss of ozone. Ozone loss rates determined using radical concentrations agree fairly well with rates calculated using a constrained photochemical model.

We compare the mixing rations of N2O, CFC-11, CFC-12, CCI4, SF6, and HCI in the mid-latitude stratosphere measured by the ATMOS Fourier transform spectrometer with in situ measurements acquired aboard the NASA ER-2 aircraft during November 1994. Good agreement is found between ATMOS and in situ correlations of CFC-11, CFC-12, and SF6 with N2O. ATMOS observations of CCI4 are approx. 15 percent higher than the ER-2 data, but within the systematic uncertainties.

The NASA Upper Atmosphere Research Program organized a Stratospheric Ozone Intercomparison Campaign (STOIC) held in July-August 1989 at the Table Mountain Facility (TMF) of the Jet Propulsion Laboratory (JPL). The primary instruments participating in this campaign were several that had been developed by NASA for the Network for the Detection of Stratospheric Change: the JPL ozone lidar at TMF, the Goddard Space Flight Center trailer-mounted ozone lidar which was moved to TMF for this comparison, and the Millitech/LaRC microwave radiometer. To assess the performance of these new instruments, a validation/intercomparison campaign was undertaken using established techniques: balloon ozonesondes launched by personnel from the Wallops Flight Facility and from NOAA Geophysical Monitoring for Climate Change (GMCC) (now Climate Monitoring and Diagnostics Laboratory), a NOAA GMCC Dobson spectrophotometer, and a Brewer spectrometer from the Atmospheric Environment Service of Canada, both being used for column as well as Umkehr profile retrievals. All of these instruments were located at TMF and measurements were made as close together in time as possible to minimize atmospheric variability as a factor in the comparisons. Daytime rocket measurements of ozone were made by Wallops Flight Facility personnel using ROCOZ-A instruments launched from San Nicholas Island. The entire campaign was conducted as a blind intercomparison, with the investigators not seeing each others data until all data had been submitted to a referee and archived at the end of the 2-week period (July 20 to August 2, 1989). Satellite data were also obtained from the Stratospheric Aerosol and Gas Experiment (SAGE 2) aboard the Earth Radiation Budget Satellite and the Total Ozone Mapping Spectrometer (TOMS) aboard Nimbus 7. An examination of the data has found excellent agreement among the techniques, especially in the 20- to 40-km range. As expected, there was little atmospheric variability during the intercomparison, allowing for detailed statistical comparisons at a high level of precision. This overview paper summarizes the campaign and provides a 'road map' to subsequent papers in this issue by the individual instrument teams which will present more detailed analysis of the data and conclusions.

This paper describes the validation of ozone data from the Upper Atmosphere Research Satellite (UARS) Microwave Limb Sounder (MLS). The MLS ozone retrievals are obtained from the calibrated microwave radiances (emission spectra) in two separate bands, at frequencies near 205 and 183 GHz.

The NASA Upper Atmosphere Research Program organized a Stratospheric Ozone Intercomparison Campaign (STOIC) held in July-August 1989 at the Table Mountain Facility (TMF) of the Jet Propulsion Laboratory (JPL).

Mid-latitude ozone data from ER-2 aircraft measurements in 1989, 1991, and 1992 were examined to determine how sulfate aerosols from the eruption of Mt. Pinatubo had affected ozone at about 18 km. N2O was used as a tracer to help distinguish between chemical and dynamical aerosol effects. At 20-45 deg N in February 1992, ozone was about 10-20% lower than February 1989 and 1991, with respect to N2O. Data from Aug. 1991 - Mar. 1992 showed changes in ozone with respect to N2O, but the magnitude of those changes was not correlated with the magnitude of the changes in aerosol surface area density.

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.

Mid-latitude ozone data from ER-2 aircraft measurements in 1989, 1991 and 1992 were examined to determine how sulfate aerosols from the eruption of Mt. Pinatubo had affected ozone at about 18 km. N2O was used as a tracer to help distinguish between chemical and dynamical aerosol effects. At 20-45 deg N in February 1992, ozone was about 10-20% lower than February 1989 and 1991, with respect to N2O. Data from Aug.1991 - Mar. 1992 showed changes in ozone with respect to N2O, but the magnitude of those changes was not correlated with the magnitude of the changes in aerosol surface area density.

Measurement made in the outer ring of the northern polar vortex from October 1991 through March 1992 reveal an altitude dependent change in ozone, with decrease at the bottom of the vortex and substantial increase at the highest altitudes accessible.

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.

The present study compares small-scale (less than 100 km) features in ER-2 measurements of ClO, O3, H2O, N2O, and NO(y) outside the lower stratospheric Arctic vortex of 1988-1989 with features on potential vorticity maps from ECMWF. The potential vorticity maps are obtained from T106 analyses and forecasts. Some of the plots were truncated to lower resolution (T63 or T42) which smooths out the finer-scale structure. Comparison of these lower resolution plots shows how much detail is lost by excessive smoothing. It is also evident that the forecast plots lose fine-scale structure due to dissipation in the model resulting mainly from horizontal diffusion. It is concluded that blobs of air on the maps at latitudes between the vortex edge and 25 deg N having potential vorticities characteristic of the vortex did indeed originate from the vortex, but that the real atmosphere is more sharply differentiated than the meteorological analyses, implying that the potential vorticity maps underestimate the amount of peeled-off material.

The Arctic polar vortex in winter is known to be chemically primed for ozone depletion, yet it does not exhibit the large seasonal ozone decrease that characterizes its southern counterpart. This difference may be due in part to a net flux of ozone-rich air through the Arctic vortex, which can mask ozone loss. But by using a chemically conserved tracer as a reference, significant ozone loss can be identified. This loss is found to be correlated with high levels of chlorine monoxide, suggesting that much of the decrease in ozone is caused by anthropogenic emissions of chlorofluorocarbons.