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Salawitch, R. J.

Publications and source records attributed to Salawitch, R. J..

96 records · Page 6

Absorption of solar radiation by O2 - Implications for O3 and lifetimes of N2O, CFCl3, and CF2Cl2

An accurate line-by-line model is used to evaluate effects of absorption in the Schumann-Runge bands of O2 on transmission of UV radiation. The model is used to evaluate rates of photolysis for N2O, CFCl3, and CF2Cl2, and to infer global loss rates and instantaneous lifetimes appropriate for 1980. A parameterized version of the line-by-line model enabling rapid evaluation of transmission in the Schumann-Runge region is described. Photochemical calculations employing the parameterization and constrained by data from the Atmospheric Trace Molecule Spectroscopy experiment are used to examine the budget of odd oxygen. Consistent with previous studies, it is shown that photochemical loss of odd oxygen exceeds production by photolysis of O2 for altitudes above 40 km. The imbalance between production and loss is shown to be consistent with a source of odd oxygen proportional to the product of the mixing ratio and photolysis rate of ozone, which suggests that processes involving vibrationally excited O2 may play an important role in production of odd oxygen.

Minschwaner, K.↗

Condensation of HNO3 on falling ice particles - Mechanism for denitrification of the polar stratosphere

Ice particles created in polar stratospheric cooling events are predicted to descend into Type I PSCs and accrete a coating of nitric acid trihydrate (NAT) that inhibits evaporation. Coated particles efficiently strip HNO3 from the atmosphere, providing a mechanism for denitrification without significant dehydration. Coatings that disintegrate may release large particles of NAT that influence subsequent particle growth.

Wofsy, S. C.↗

Denitrification in the Antarctic stratosphere

Rapid loss of ozone over Antarctica in spring requires that the abundance of gaseous nitric acid be very low. Precipitation of particulate nitric acid has been assumed to occur in association with large ice crystals, requiring significant removal of H2O and temperatures well below the frost point. However, stratospheric clouds exhibit a bimodal size distribution in the Antarctic atmosphere, with most of the nitrate concentrated in particles with radii of 1 micron or greater. It is argued here that the bimodal size distribution sets the stage for efficient denitrification, with nitrate particles either falling on their own or serving as nuclei for the condensation of ice. Denitrification can therefore occur without significant dehydration, and it is unnecessary for temperatures to drop significantly below the frost point.

Salawitch, R. J.↗

The chemistry of Antarctic ozone 1960-1987

The factors that influence Antarctic ozone are examined with a view to understanding the observed historical trend. Researchers show that reduced ambient temperatures can dramatically enhance the efficiency of chemical removal processes. Attention is focused on positive feedback between levels of ozone, temperature, and rates of heterogeneous chemical reactions. ClO and its dimer, and high levels of these gases are maintained until the clouds evaporate, on 15 September for the simulation shown here.

Salawitch, R. J.↗

Interactions between HCl, NO(x), and H2O ice in the Antarctic stratosphere - Implications for ozone

The role of PSC particles in determining the distributions of HCl and chlorine radicals is studied. The thermodynamics of HCl in ice is discussed, showing that significant quantities of HCl may be dissolved in ice when PSCs form. It is argued that HCl and HNO3 will be removed from the gas phase early in the condensation process, when only small quantities of H2O have been condensed, reflecting the thermodynamic properties of the solid phases of HCl, HNO3, and H2O. Rapid heterogeneous chemical reactions then volatilize reactive chlorine gases and convert NO(x) to solid-phase nitrates, which can be removed by gravitational settling. Analysis of the suite of heterogeneous chemical processes in the polar stratosphere implies a threshold for HCl concentrations, above which chemical loss rates for ozone increase dramatically.

Wofsy, S. C.↗

Reductions of Antarctic ozone due to synergistic interactions of chlorine and bromine

The vertical column density of ozone observed in October over Antarctica has fallen precipitously over the past 10 yr. The concentration at Halley Bay (76 deg S, 27 deg W), expressed conventionally in Dobson units (DU), has dropped from about 300 DU in 1975 to less than 200 DU in 1984. Values in 1985 were even lower, comparable with the lowest values recorded anywhere on earth. It is suggested here that the loss of O3 in Antarctica may be attributed to catalysis of O3 recombination by a scheme in which the rate-limiting step is defined by the reaction of ClO + BrO - Cl + Br + O2. Concentrations of NO2 must be low and heterogeneous reactions involving particles in the polar stratospheric clouds must be an important element of the relevant chemistry. Industrial sources make important contributions to the contemporary budgets of both BrO and ClO and are likely to grow significantly in the future.

Mcelroy, M. B.↗