Effect of clouds on the photodissociation of NO2: Observations and modelling

The role of clouds in photodissociation is examined by both modelling and observations. It is emphasized that the photodissociation rate is proportional to the actinic flux rather than to the irradiance. The actinic flux concerns the energy that is incident on a molecule, irrespective of the direction of incidence. The irradiance concerns the energy that is incident on a plane.As far as the modelling aspect is concerned, a multi-layer delta-Eddington model is used to calculate irradiances, actinic fluxes, and photodissociation rates of nitrogen dioxide J(NO₂) as a function of height in inhomogeneous atmospheres. For the considered wavelength interval [290–420 nm], Rayleigh scattering, ozone absorption, and Mie scattering and absorption by cloud drops and aerosols should be taken into account.Further, a three-layer model is used to calculate the actinic flux above and below a cloud, relative to the incident flux, in terms of cloud albedo, zenith angle, and the albedo of the underlying and overlying atmosphere. Cloud albedo is mainly determined by cloud optical thickness. An expression for the incloud actinic flux is given as a function of in-cloud optical thickness. The three-layer model seems to be a useful model for the estimation of photodissociation rates in dispersion models.It is stressed that both models in their present form cannot handle partial cloudiness.It is shown that if no clouds are present, the actinic flux depends primarily on solar zenith angle. Further, the incident flux at the top of the atmosphere diminishes downward into the atmosphere due to the increasing effect of scattering. Therefore, the actinic flux usually increases with height, although above clouds the actinic flux sometimes decreases with height due to a large contribution of the upward scattered light.For cloudy atmospheres, another important parameter with respect to the actinic flux is added: cloud optical thickness. Cloud optical thickness determines cloud albedo. It can be shown that incloud characteristics and cloud height are less important while describing the effect of a cloud on the actinic flux (outside the cloud). The in-cloud values of the actinic flux can exceed the values outside the cloud.Finally, using the photostationary state relationship, a comparison is performed between model results and ground-based measurements as well as in-cloud air craft measurements.