Evaluation of Novel Routes for NO_x Formation in Remote Regions

Photochemical cycling of nitrogen oxides (NO_x) produces tropospheric ozone (O₃), and NO_x is traditionally considered to be directly emitted. The inability of current global models to accurately calculate NO_x levels, and concurrently, difficulties in performing direct NO_x measurements in low-NO_x regimes (several pptv or several tens of pptv) globally introduce a large uncertainty in the modeling of O₃ formation. Here, we use the near-explicit Master Chemical Mechanism (MCM v3.2) within a 0D box-model framework, to describe the chemistry of NO_x and O₃ in the remote marine boundary layer at Cape Verde. We explore the impact of a recently discovered NO_x recycling route, namely photolysis of particulate nitrate, on the modeling of NO_x abundance and O₃ formation. The model is constrained to observations of long-lived species, meteorological parameters, and photolysis frequencies. Only a model with this novel NO_x recycling route reproduces levels of gaseous nitrous acid, NO, and NO₂ within the model and measurement uncertainty. O₃ formation from NO oxidation is several times more efficient than previously considered. This study highlights the need for the inclusion of particulate nitrate photolysis in future models for O₃ and for the photolysis rate of particulate nitrate to be quantified under variable atmospheric conditions.