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

K. Minschwaner, R. J. Salawitch, M. B. McElroy

doi:10.1029/93jd00223

<jats:p>An accurate line‐by‐line model is used to evaluate effects of absorption in the Schumann‐Runge bands of O<jats:sub>2</jats:sub> on transmission of ultraviolet radiation. Allowing also for absorption in the Herzberg continuum, the model is shown to provide a reliable simulation of observed transmission in the spectral interval 192 to 200 nm. The model is used to evaluate rates for photolysis of N<jats:sub>2</jats:sub>O, CFCl<jats:sub>3</jats:sub>, and CF<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>, and to infer global loss rates (1.22×l0<jats:sup>10</jats:sup> kg N yr<jats:sup>−1</jats:sup>, 7.21×10<jats:sup>7</jats:sup> and 3.04×l0<jats:sup>7</jats:sup> kg Cl yr<jats:sup>−1</jats:sup>, respectively) and instantaneous lifetimes (123, 44, and 116 years, respectively) 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 O<jats:sub>2</jats:sub> 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 O<jats:sub>2</jats:sub> may play an important role in production of odd oxygen.</jats:p>

Absorption of solar radiation by O<sub>2</sub>: Implications for O<sub>3</sub> and lifetimes of N<sub>2</sub>O, CFCl<sub>3</sub>, and CF<sub>2</sub>Cl<sub>2</sub>

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