Rapid cycling of reactive nitrogen in the marine boundary layer

Aircraft measurements, laboratory photolysis experiments and modelling calculations reveal a mechanism for the recycling of nitric acid into nitrogen oxides; this enables observations to be reconciled with model studies, and suggests that particulate nitrate photolysis could be a substantial tropospheric nitrogen oxide source. Rapid NO x recycling in marine air Nitrogen oxides play a central role in tropospheric chemistry, but current understanding of the processes responsible for their formation and removal from the atmosphere is insufficient to reconcile model studies with observations. This paper presents aircraft measurements, laboratory photolysis experiments and modelling calculations that reveal a mechanism for the rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. The authors suggest that this process could be an important tropospheric nitrogen oxide source in remote oceanic regions with implications for tropospheric oxidant and secondary atmospheric aerosol formation. Nitrogen oxides are essential for the formation of secondary atmospheric aerosols and of atmospheric oxidants such as ozone and the hydroxyl radical, which controls the self-cleansing capacity of the atmosphere 1 . Nitric acid, a major oxidation product of nitrogen oxides, has traditionally been considered to be a permanent sink of nitrogen oxides 1 . However, model studies predict higher ratios of nitric acid to nitrogen oxides in the troposphere than are observed 2 , 3 . A ‘renoxification’ process that recycles nitric acid into nitrogen oxides has been proposed to reconcile observations with model studies 2 , 3 , 4 , but the mechanisms responsible for this process remain uncertain 5 , 6 , 7 , 8 , 9 . Here we present data from an aircraft measurement campaign over the North Atlantic Ocean and find evidence for rapid recycling of nitric acid to nitrous acid and nitrogen oxides in the clean marine boundary layer via particulate nitrate photolysis. Laboratory experiments further demonstrate the photolysis of particulate nitrate collected on filters at a rate more than two orders of magnitude greater than that of gaseous nitric acid, with nitrous acid as the main product. Box model calculations based on the Master Chemical Mechanism 10 , 11 suggest that particulate nitrate photolysis mainly sustains the observed levels of nitrous acid and nitrogen oxides at midday under typical marine boundary layer c