Actinometric and radiometric measurement and modeling of the photolysis rate coefficient of ozone to O (^1D) during Mauna Loa Observatory Photochemistry Experiment 2

The in situ photolysis rate coefficient of O3 to O(1D) has been measured at Mauna Loa Observatory using a new actinometric instrument based on the reaction of O(1D) with N2O and with a hemispherical radiometer. One minute averaged photolysis rate coefficients were determined with an overall uncertainty of approximately ±11% at the 1 σ level for the actinometer and ±15% at the 1 σ level for the radiometer. Over 120 days of data were collected with varying cloud cover, aerosol loadings, and overhead ozone representing the first set of long term measurements. Clear sky solar noon values vary between approximately 3.0 × 10−5 and 4.5 × 10−5 sec−1. Modeling of the photolysis rate coefficients was done using a discrete ordinate radiative transfer scheme and results were compared with the actinometric measurements. The quantum yields for O(1D) production are reevaluated from existing data and reported here. The comparisons were done using the quantum yields for the photolysis of ozone recommended by DeMore et al. [1994], the newer evaluation of Michelsen et al. [1994], and also with reevaluated values in this paper. An analysis of the measured photolysis rate coefficient of O3 to O(1D) and model simulations of the photolysis rate coefficient data from clear days during the study provides added insight into the choice of quantum yield data for use in photochemical models of the troposphere.

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