Transformation of irradiance measurements into spectral actinic flux for photolysis rates determination

Abstract

The actinic flux is the only radiometric quantity suitable for photolysisfrequency determination. It is derived from solar spectral irradiancemeasurements performed by a portable spectroradiometer in the 300–850nm wavelength range. The spectral irradiance is first divided into a directpart and a diffuse part, according to the atmospheric conditions, and thenconverted into the corresponding actinic flux quantity. As an intermediary,the ratio $$r_{dd} $$ of diffuse actinic flux to diffuseirradiance is calculated by the spherical harmonics radiative code withrespect to wavelength, solar zenith angle, surface albedo, and aerosolproperties.The results of extensive sensitivity studies of $$r_{dd} $$ asa function of the main atmospheric parameters are discussed and lead to theconclusion that aerosol optical depth is the major critical value for aprecise $$r_{dd} $$ determination. The global algorithm totransform spectral irradiance into actinic flux is finally applied forphotodissociation rate calculations by convolution of the obtained actinicflux spectra with the absorption cross-sections and quantum yields of themolecule studied. Photolysis rates of different atmospheric photooxidants havebeen measured with this spectroradiometric method during the summers of 1993and 1994 in Brittany and in Portugal. The ozone and nitrogen dioxidephotodissociation rates obtained present a good agreement with thej(O3) and j(NO2) actinometerresults, for the same experimental conditions in Brittany.