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POAM solar occultation observations from 1994 to present are studied for the purpose of determining Type I PSC formation characteristics and winter-long evolution. This study examines PSC observations from many years on a common basis to see if characteristics can be identified. The results show that Type Ia PSCs form at the beginning of the winter, within several days of the first drop in temperature below T_NAT, and peak early in the winter. Type Ia PSCs typically out number Ib PSCs over the winter, especially at the beginning of the winter. Type Ia and Ib PSC observations continue throughout the winter. Micro-physical models of PSC formation must match these observed characteristics. Some models predict that temperatures must be more than 5 K below T_NAT for five days before significant freezing can occur. This is not seen in the POAM observations. Differences in PSC characteristics between the first two Arctic winters (1994-1995 and 1995-1996) and later winters also suggest the influence of volcanic perturbations on PSC formation. Type Ia and Ib PSC Characteristics observed by POAM III and SAGE III for the 2002-2003 Arctic winter are compared.

POAM solar occultation observations from1994 to present are studied for the purpose of determining Type I PSC formation characteristics and winter-long evolution. This information is critical to an improved understanding and predictive capability of stratospheric ozone depletion. Solar occultation satellite observations of these clouds yields more continuous and wide-spread information than can be obtained from aircraft, balloon, or ground-based observations. This multi-winter PSC study is augmented by the use of our Type Ia/Ib discrimination scheme. Recent studies of PSC formation made with POAM observations and simulations during the 1999-2000 Arctic winter have shown characteristics that shed light on the formation mechanisms responsible for Type Ia solid phase PSCs. This study examines PSC observations from many years on a common basis to see if the characteristics observed & cuing the 1999-2000 Arctic winter ai-e observed in other years and if other characteristics can be identified. The results show that Type Ia PSCs form at the beginning of the winter, within several days of the fxst drop in temperature below TNAT, and peak early in the winter. Type Ia PSCs typically outnumber Ib PSCs over the winter, especially at the beginning of the winter. Type Ia and Ib PSC observations continue throughout the winter. Micro-physical models of PSC formation must match these observed characteristics. Some models predict that temperatures must be more 5 K below T-NAT for five days before significant freezing can occur. This is not seen in the POAM observations. Differences in PSC characte ristics between the first two Arctic winters (1 994- 1995 and 1995- 1 996) and later winters also suggest the influence of volcanic perturb ations on PSC formation. Type Ia and Ib PSC characteristics observed by POAM III and SAGE III for the 2002-2003 Arctic winter are compared.

Simulations of the 1999-2000 winter have tested the effect on polar stratospheric clouds (PSCs) of the homogeneous freezing of liquid ternary solutions into nitric acid trihydrate (NAT) and nitric acid dihydrate (NAD). Proposed laboratory-derived volume-based and surface-based homogeneous freezing rates have both been examined, including different assumptions about the extrapolation of laboratory measurements to atmospheric conditions. Widespread PSC formation and denitrification are possible in several of the scenarios examined. However, the simulations are all unable to explain the solid-phase PSCs observed early in the 1999-2000 winter, and are unable to reproduce the measured extent of vortex denitrification. These problems can both be attributed to the relatively cold temperatures, more than 5 K below the NAT condensation point, necessary for effective homogeneous freezing. Therefore synoptic-scale homogeneous freezing appears unlikely to be the primary mechanism responsible for solid-phase PSC formation.

Model simulations have been used to analyze the factors influencing ozone loss during the 1999-2000 and 2002-2003 js. For both winters, the evolution of the Arctic vortex from November to April has been simulated using a trajectory-based microphysical and photochemical model. Extensive PSC formation and strong ozone depletion are evident in both winters. However, the ozone loss begins earlier in the 2002-2003 winter, with significant ozone depletion by early January. Analysis of the model results shows that during December 2002 not only cold temperatures but also the vortex structure was critical, allowing PSC-processed air parcels to experience significant solar exposure. The resultant ozone loss can be differentiated from ozone loss that occurs in the springtime, in particular because of the continued exposure to PSCs. For example, chlorine reactivation by the PSCs causes ozone loss to be insensitive to denitrification. Therefore, diagnosing the extent of ozone loss early in the winter is critical In understanding the overall winter-long ozone depletion.

A better knowledge of PSC composition and formation mechanisms is important to better understand and predict stratospheric ozone depletion. Several past studies have attempted to compare modeling results with satellite observations. These comparisons have concentrated on case studies. In this paper we adopt a statistical approach. POAM PSC observations from several Arctic winters are categorized into Type Ia and Ib PSCs using a technique based on Strawa et al. The discrimination technique has been modified to employ the wavelengths dependence of the extinction signal at all wavelengths rather than only at 603 and 10 18 nm. Winter-long simulations for the 1999-2000 Arctic winter have been made using the IMPACT model. These simulations have been constrained by aircraft observations made during the SOLVE/THESEO 2000 campaign. A complete set of winter-long simulations was run for several different microphysical and PSC formation scenarios. The simulations give us perfect knowledge of PSC type (Ia, Ib, or II), composition, especially condensed phase HNO3 which is important for denitrification, and condensed phase H2O. Comparisons are made between the simulation and observation of PSC extinction at 1018 rim versus wavelength dependence, winter-long percentages of Ia and Ib occurrence, and temporal and altitude trends of the PSCs. These comparisons allow us to comment on how realistic some modeling scenarios are.

Winter-long simulations of the 1999-2000 winter using a coupled microphysical/chemical model have been carried out to explore how PSC microphysics affects ozone loss. Although many models assures that water ice formation leads to denitrification, these simulations show that observed characteristics of the 1999-2000 winter can not be reproduced by such a denitrification mechanism. Instead, denitrification observations are best reproduced by a small number of particles freezing at temperatures near the nitric acid trihydration condensation point. Implications of such a mechanism for assessments of future ozone loss will be discussed. The simulations have also revealed that ozone loss during the 1999-2000 winter was sensitive to chlorine reactivation that occurred during February. Uncertainties in PSC microphysics and heterogeneous reaction rates both influence the modelled chlorine reactivation. For the 1999-2000 winter, these uncertainties have a larger effect on model ozone loss than denitrification. The role of denitrification would have increased if the Arctic vortex had persisted for a longer period.

Type Ia PSCs are believed to be composed of nitric acid hydrate particles. Recent results from the SOLVE/THESEO 2000 campaign showed evidence that this type of PSC was composed of a small number of very large particles capable of sedimentary denitrification of regions of the stratosphere. It is unknown whether homogeneous or heterogeneous nucleation is responsible for the formation of these PSCs. Arctic winters are tending to be colder in response to global tropospheric warming. The degree to which this influences ozone depletion will depend on the freezing mechanism of nitric acid hydrate particles. If nucleation is homogeneous it implies that the freezing process is an inherent property of the particle, while heterogeneous freezing means that the extent of PSCs will depend in part on the number of nuclei available. The Polar Ozone and Aerosol Measurement (POAM)II and III satellites have been making observations of stratospheric aerosols and Polar Stratospheric Clouds (PSCs) since 1994. Recently, we have developed a technique that can discriminate between Type Ia and Ib PSCs using these observations. A statistical approach is employed to demonstrate the robustness of this approach and results are compared with lidar measurements. The technique is used to analyze observations from POAM II and II during Northern Hemisphere winters where significant PSC formation occurred with the objective of exploring Type I PSC formation mechanisms. The different PSCs identified using this method exhibit different growth curve as expressed as extinction versus temperature.

Stratospheric hydration and dehydration were measured inside the Arctic polar vortex in January and February 2000, as part of the Sage III Ozone Loss Validation Experiment (SOLVE).

The effect of a range of assumptions about polar stratospheric clouds (PSCs) on ozone depletion has been assessed using at couple microphysical/photochemical model. The composition of the PSCs was varied (ternary solutions, nitric acid trihydrate, nitric acid dehydrate, or ice), as were parameters that affected the levels of denitrification and dehydration. Ozone depletion was affected by assumptions about PSC freezing because of the variability in resultant nitrification chlorine activation in all scenarios was similar despite the range of assumed PSC compositions. Vortex-average ozone loss exceeded 40% in the lower stratosphere for simulations without nitrification an additional ozone loss of 15-20% was possible in scenarios where vortex-average nitrification reached 60%. Ozone loss intensifies non-linearly with enhanced nitrification in air parcels with 90% nitrification 40% ozone loss in mid-April can be attributed to nitrification alone. However, these effects are sensitive to the stability of the vortex in springtime: nitrification only began to influence ozone depletion in mid-March.

Trajectory cloud model calculations are presented to show that homogeneous freezing of nitric acid hydrates can produce a polar freezing belt in both hemispheres that can cause denitrification. While hydrate cloud microphysical properties are similar over both poles, the shorter persistence of clouds in the Arctic prevents the depth of the denitrified layers from growing beyond a few kilometers. The 1999-2000 Arctic winter is unique in showing a distinct denitrification profile with a depth of approx. 4.5 km that is nearly half as deep as that computed for a typical Antarctic winter.

In-situ Multi-Angle Spectrometer Probe (MASP) particle measurements have been analyzed to determine the typical behaviour of sulphate particles during the SOLVE campaign. The analysis has focussed on variations in the total particle concentration measured by MASP, which is a diagnostic that is primarily sensitive to the growth of small particles (those which are initially smaller than 0.2 micrometers in radius). At all levels of the stratosphere, the total MASP concentration varies continuously with temperature. This behaviour is well-reproduced by assuming that the sulphate aerosols are liquid ternary solutions, but cannot be reproduced if the aerosol is assumed to be frozen. This liquid-like behaviour is apparent for all measurements made during SOLVE, both inside and outside the vortex, and even at the coldest temperatures sampled during the campaign. The only anomalous measurements were made during the flight of January 14th, 2001; however, this midlatitude flight is very unlikely to contain SAT particles based on the recent warm temperatures experienced by the air. At the levels with the coldest measured temperatures, at least 90% of the particles grow as liquids. Therefore, the freezing that occurred during the 1999-2000 Arctic winter was selective, causing most of the particles to remain liquid even in the presence of a small number of frozen particles.

Stratospheric aerosol can affect the environment in three ways. Sulfuric acid aerosol have been shown to act as sites for the reduction of reactive nitrogen and chlorine and as condensation sites to form Polar Stratospheric Clouds, under very cold conditions, which facilitate ozone depletion. Recently, modeling studies have suggested a link between BCA (Black Carbon Aerosol) and ozone chemistry. These studies suggest that HNO3, NO2, and O3 may be reduced heterogeneously on BCA particles. The ozone reaction converts ozone to oxygen molecules, while HNO3 and NO2 react to form NOx. Finally, a buildup of BCA could reduce the single-scatter albedo of aerosol below a value of 0.98, a critical value that has been postulated to change the effect of stratospheric aerosol from cooling to warming. Correlations between measured BCA amounts and aircraft usage have been reported. Attempts to link BCA to ozone chemistry and other stratospheric processes have been hindered by questions concerning the amount of BCA that exists in the stratosphere, the magnitude of reaction probabilities, and the scarcity of BCA measurements. The Ames Wire Impactors (AWI) participated in POLARIS as part of the complement of experiments on the NASA ER-2. One of our main objectives was to determine the amount of aerosol surface area, particularly BCA, available for reaction with stratospheric constituents and assess if possible, the importance of these reactions. The AWI collects aerosol and BCA particles on thin Palladium wires that are exposed to the ambient air in a controlled manner. The samples are returned to the laboratory for subsequent analysis. The product of the AWI analysis is the size, surface area, and volume distributions, morphology and elemental composition of aerosol and BCA. This paper presents results from our experiments during POLARIS and puts these measurements in the context of POLARIS and other missions in which we have participated. It describes modifications to the AWI data analysis procedures in which the collection of BCA is modeled as a fractal aggregate. The new analysis results in an increase in BCA surface area of approximately 24 and an increase in mass of 7-10 from the previous method. For the current study, BCA surface area is used in computer models that attempt to predict measured NOx/NOy ratios and O3 depletion rates. Inclusion of the HNO3 reaction with BCA in one model tends to improve the agreement of calculated to measured NOx/NOy ratio. However, it was found that these trends are viable only if the reactions are catalytic.

During the Arctic Airborne Stratospheric Expedition (AASE) simultaneous measurements of aerosol size distribution and NO(y)(HN03 + NO + NO2 + 2(N205)) were made along ER-2 flight paths. The flow characteristics of the NO(y) instrument allow us to derive the condensed NO(y) amount (assumed to be HN03) present during polar stratospheric cloud (PSC) events. Analysis of the January 24th flight indicates that this condensed HN03 amount does not agree well with the aerosol volume if the observed PSCs are composed of solid nitric acid trihydrate (NAT), as is generally assumed. However, the composition agrees well with that predicted for liquid H2S04/HN03/H20 solution droplets using a new Aerosol Physical Chemistry Model (APCM). The agreement corresponds in detail to variations in temperature and humidity. The weight percentages of H2SO4, HN03, and H2O derived from the measurements all correspond to those predicted for ternary, liquid solutions.

Mechanisms for the formation of Type I (nitric acid-based) polar stratospheric clouds (PSCs) are discussed. If the pre-existing sulfate aerosols are liquid prior to PSC formation, then nitric acid particles (Type Ib) form by HNO3 dissolution in aqueous H2SO4 solution droplets. This process does not require a nucleation step for the formation of HNO3 aerosols, so most pre-existing aerosols grow to become relatively small HNO3-containing particles. At significantly lower temperatures, the resulting supercooled solutions (Type Ib) may freeze to form HNO3 ice particles (Type Ia). If the pre-existing sulfate aerosols are initially solid before PSC formation, then HNO3 vapor can be deposited directly on the frozen sulfate particles. However, because an energy barrier to the condensation exists a nucleation mechanism is involved. Here, we suggest a unique nucleation mechanism that involves formation of HNO3/H20 solutions on the sulfate ice particles. These nucleation processes may be highly selective, resulting in the formation of relatively small number of large particles.

A detailed model of polar stratospheric clouds (PSCs), which includes nucleation, condensational growth. and sedimentation processes, has been applied to the study of heterogeneous chemical reactions. For the first time, the extent of chemical processing during a polar winter has been estimated for an idealized air parcel in the Antarctic vortex by calculating in detail the rates of heterogeneous reactions on PSC particles. The resulting active chlorine and NO(x) concentrations at first sunrise are analyzed with respect to their influence upon the Antarctic ozone hole using a photochemical model. It is found that the species present at sunrise are primarily influenced by the relative values of the heterogeneous reaction rate constants and the initial gas concentrations. However, the extent of chlorine activation is also influenced by whether N2O5 is removed by reaction with HCl or H2O. The reaction of N2O5 with HCl, which occurs rapidly on type 1 PSCs, activates the chlorine contained in the reservoir species HCl. Hence the presence and surface area of type 1 PSCs early in the winter are crucial in determining ozone depletion.