The collisions between two oxygen molecules give rise to O4 absorption in the Earth atmosphere. O4 absorption is relevant to atmospheric transmission and Earth’s radiation budget. O4 is further used as a reference gas in Differential Optical Absorption Spectroscopy (DOAS) applications to infer properties of clouds and aerosols. The O4 absorption cross section spectrum of bands centered at 343, 360, 380, 446, 477, 532, 577 and 630 nm is investigated in dry air and oxygen as a function of temperature (203–295°K), and at 820 mbar pressure. We characterize the temperature dependent O4 line shape and provide high precision O4 absorption cross section reference spectra that are suitable for atmospheric O4 measurements. The peak absorption cross-section is found to increase at lower temperatures due to a corresponding narrowing of the spectral band width, while the integrated cross-section remains constant (within o3%, the uncertainty of our measurements). The enthalpy of formation is determined to be ΔH250 = -0.12±0.12 kJ mol-1, which is essentially zero, and supports previous assignments of O4 as collision induced absorption (CIA). At 203°K, van der Waals complexes (O2-dimer) contribute less than 0.14% to the O4 absorption in air. We conclude that O2-dimer is not observable in the Earth atmosphere, and as a consequence the atmospheric O4 distribution is for all practical means and purposes independent of temperature, and can be predicted with an accuracy of better than 10-3 from knowledge of the oxygen concentration profile.
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Atmospheric observations of the O4 absorption bands at 360.5, 380.2, 477.3, 532.2, 577.2 and 630.0 nm are presented for different atmospheric conditions (clear and cloudy skies) and viewing geometries (direct and zenith-scattered light observations). From the observations of direct moonlight it was possible to derive absolute O4 absorption cross sections for atmospheric conditions. We found that the relative shape of the observed absorption bands is similar to those of the O4 spectrum measured by Greenblatt et al. [1990] in the laboratory. However, in general (except for the absorption band at 380.2 nm), the O4 absorption cross sections derived in this study are larger by several percent compared to those of the other (mainly laboratory) observations. Using the observations of zenith-scattered light, we investigated the radiative transport through the atmosphere. Our observations under cloudy sky conditions confirmed that the light path enhancement due to multiple Mie scattering on cloud droplets is independent of wavelength. From the observations under clear-sky conditions we studied the influence of Mie scattering on aerosol. It was not possible to describe the selected clear-sky measurements by taking into account only Rayleigh scattering. We found that the comparison of the O4 measurements with model results for different sets of assumed aerosol extinctions provides a new, very sensitive tool to derive aerosol parameters from zenith sky ground-based measurements.
