Oxidation photochemistry in the Southern Atlantic boundary layer: Unexpected deviations of photochemical steady state

Ozone (O[subscript 3]) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O[subscript 3] loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO[subscript 2], O[subscript 3], J[subscript NO2], J(O[superscript 1]D), HO[subscript 2], OH, RO[subscript x] and a range of meteorological parameters were carried out. The concentrations of NO and NO[subscript 2] measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NO[subscript x] conditions (5–25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NO[subscript x] mixing ratio and J[subscript NO2] intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NO[subscript x] (NO + NO[subscript 2]) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO[subscript 2] radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°–60° S over the Atlantic Ocean.