Twilight observations suggest unknown sources of HO_x

Abstract

Measurements of the concentrations of OH and HO_(2) (HO_(x)) in the high-latitude lower stratosphere imply the existence of unknown photolytic sources of HO_(x). The strength of the additional HO_(x) source required to match the observations depends only weakly on solar zenith angle (SZA) for 80° < SZA < 93°. The wavelengths responsible for producing this HO_(x) must be longer than 650 nm because the flux at shorter wavelengths is significantly attenuated at high SZA by scattering and absorption. Provided that the sources involve only a single photon, the strength of the bonds being broken must be < 45 kcal mole^(−1). We speculate that peroxynitric acid (HNO_4) dissociates after excitation to an unknown excited state with an integrated band cross section of 2-3 × 10^(−20) cm^(2) molecule^(−1) nm (650 < λ < 1250 nm).