ALBERT

Description: It is well known that many chlorine and bromine compounds that are inert in the troposphere are destroyed in the stratosphere and contribute to the stratospheric burden of reactive chlorine and bromine species. But the contribution from those chlorine and bromine compounds which are reactive in the troposphere is less certain because it is not known whether convection can transport these gases to the upper troposphere rapidly enough to overcome their short tropospheric lifetimes. We examine this issue using a three-dimensional chemistry and transport model to simulate the evolution of three gases which have surface sources, bromoform (CHBr3), methyl chloroform (CH3CCl3), and carbon dioxide (CO2). Our objective is to determine if CHBr3 might enhance the lower stratospheric burden of reactive bromine. The other two gases provide tests of the quality of the simulation. Both CHBr3 and CH3CCl3 are destroyed in the troposphere by reaction with hydroxyl (OH), whose latitudinal and monthly variation is provided by a two-dimensional model and upon which a diurnal variation is imposed. Comparison of the lifetime of CH3CCl3 computed from observations (5 years) with the lifetime computed from the simulation provides an integrated test of the model's transport and photochemistry. Observations also show that CO2 exhibits a strong seasonal cycle in the northern hemisphere troposphere that is not propagated directly across the tropopause into the lower stratosphere. Thus, maintenance of the observed troposphere-stratosphere distinctness of CO2 in the presence of convection is a critical benchmark for meeting our objective.

Description: We have investigated the middle atmospheric response to the 27-day and 11-yr solar UV flux variations at low to middle latitudes using a two-dimensional photochemical model. The model reproduced most features of the observed 27-day sensitivity and phase lag of the profile ozone response in the upper stratosphere and lower mesosphere, with a maximum sensitivity of +0.51% per 1% change in 205 nm flux. The model also reproduced the observed transition to a negative phase lag above 2 mb, reflecting the increasing importance with height of the solar modulated HO(x) chemistry on the ozone response above 45 km. The model revealed the general anti-correlation of ozone and solar UV at 65-75 km, and simulated strong UV responses of water vapor and HO(x) species in the mesosphere. Consistent with previous 1D model studies, the observed upper mesospheric positive ozone response averaged over +/- 40 was simulated only when the model water vapor concentrations above 75 km were significantly reduced relative to current observations. In agreement with observations, the model computed a low to middle latitude total ozone phase lag of +3 days and a sensitivity of +0.077% per 1% change in 205 nm flux for the 27-day solar variation, and a total ozone sensitivity of +0.27% for the 11-yr solar cycle. This factor of 3 sensitivity difference is indicative of the photochemical time constant for ozone in the lower stratosphere which is comparable to the 27-day solar rotation period but is much shorter than the 11-yr solar cycle.

Description: The effects of heterogeneous processing by a parameterized lower stratospheric sulfate aerosol layer on model calculations were examined using a 2D photochemical model. Model results were compared with zonally averaged LIMS data on HNO3 and NO2 and in situ measurements of NO, NO(y), and ClO, taken by the ER-2 aircraft. The results obtained are contradictory: some comparisons favor heterogeneous chemistry, and some do not. It is suggested that the assumptions made to parameterize the sulfate aerosol chemistry result in a rate of heterogeneous processing that is too vigorous.

Description: Three-dimensional model simulations are used to describe the January 31, 1989 ozone minihole over Stavanger, Norway. This minihole is typical of many transient events in the lower stratosphere that arise because of cyclonic-scale disturbances in the troposphere. Although the ozone reduction is a short-lived reversible dynamical event, through heterogeneous chemical processes there can be a significant transfer of chlorine from reservoir molecules to active radicals. This chemically perturbed air is defined as processed air, and it is found that a single event can produce enough processed air to reduce the HCl in the entire polar vortex. Chemical processing on clouds associated with transient events is shown to be a major source of processed air in the polar vortex in December before background temperatures are cold enough for more uniform heterogeneous conversion.

Description: This section contains a number of special diagnostics that are designed to examine certain mechanisms. Section 1 reports on the method used to test the photochemical partitioning in the models. Sections 2 and 3 represent efforts to examine the model calculated production and removal rates for ozone and how the values are combined with transport rates in the models to produce the simulated ozone distributions. Sections 4 and 5 concentrate on polar processes including the dynamics aspect of vortex confinement and the chemical aspects of chlorine activation.

Description: The application of van Leer's scheme, a monotonic, upstream-biased differencing scheme, to three-dimensional constituent transport calculations is shown. The major disadvantage of the scheme is shown to be a self-limiting diffusion. A major advantage of the scheme is shown to be its ability to maintain constituent correlations. The scheme is adapted for a spherical coordinate system with a hybrid sigma-pressure coordinate in the vertical. Special consideration is given to cross-polar flow. The vertical wind calculation is shown to be extremely sensitive to the method of calculating the divergence. This sensitivity implies that a vertical wind formulation consistent with the transport scheme is essential for accurate transport calculations. The computational savings of the time-splitting method used to solve this equation are shown. Finally, the capabilities of this scheme are illustrated by an ozone transport and chemistry model simulation.

Description: The evolution of ozone has been calculated for the winters of 1979 and 1989 using winds derived from the stratospheric data assimilation system STRATAN. The ozone fields calculated using this technique are found to compare well with satellite-measured fields for simulations of 2-3 months. This paper presents comparisons of model fields with both satellite and sonde measurements to verify that stratospheric transport processes are properly represented by this modeling technique. Attention is focused on the Northern Hemisphere middle and high latitudes at the 10-hPa level and below, where transport processes are most important to the ozone distribution. First-order quantities and derived budgets from both the model and satellite data are presented. By sampling the model with a limb-viewing satellite and then Kalman filtering the 'observations' of the model, it is shown that transient subplanetary-scale features that are essential to the ozone budget are missed by the satellite system.

Description: This paper investigates the effects of solar proton events (SPEs) on the middle atmosphere during the past two solar cycles (1963-1984), by examining changes in the production of odd nitrogen, NO(y), and ozone and using a proton energy degradation scheme to derive ion pair production rates. These calculations show that NO(y) is not substantially changed over a solar cycle by SPEs; significant SPEs last only 1-5 days, tend to occur near solar maximum, and are typically months to years apart, preventing a build up of SPE-produced NO(y). Fractional ozone changes are even smaller than the fractional NO(y) changes and are significant only for the August 1972 SPE. Ozone, like NO(y), returns to its ambient levels on time scales of several months to a year.

Description: Simulations of the spatial and temporal variability of the extent of chemically processed air in the Arctic stratosphere have been carried out using a three-dimensional chemistry-transport model for the winters of 1979 and 1989. Chemically processed air is identified in the model as that in which the amounts of hydrogen chloride (HCl) calculated with parameterized loss for conditions appropriate to polar stratospheric cloud (PSC) formation are substantially smaller than those calculated in a model with gas phase chemistry only. It is seen that chemically processed air may be identified over much of the Arctic lower stratosphere from early January to late February, with HCl depletions being larger in 1989 than in 1979. Near the latitude of the Arctic circle, there is important spatial and temporal variability in the extent of chemically processed air. There is some evidence for transport to midlatitudes of processed air during these winters, but the HCl reductions are much smaller and more sporadic than those near the pole. At 62 and 42N, processed air is calculated to occur preferentially over the longitude regions from 60-120E and 270-330E.

Description: Three-dimensional model calculations with the NASA/GSFC chemistry and transport model have been designed to consider the impact of heterogeneous processes occurring on polar stratospheric clouds (PSCs) in the Arctic vortex on the HCl distribution. By examining the HCl concentration for a calculation with PSCs relative to a calculation with gas phase chemistry only, the impact of polar processing on reactive chlorine species at middle latitudes is inferred. Results from the chemistry and transport model reproduce basic features of the ClO measurements (Toohey et al., 1991), which were made on the ferry flights of the ER-2 from Stavanger, Norway to Moffett Field, California via Wallops Island, Virginia on February 20 and 21, 1989. The model indicates that perturbed air which is contained within the polar vortex during winter is not homogeneously mixed, and that the ferry flights were made through air with the largest conversion of HCl to reactive chlorine that is seen at middle latitudes.