A controlling role for the air−sea interface in the chemical processing of reactive nitrogen in the coastal marine boundary layer

The lifetime of reactive nitrogen and the production rate of reactive halogens in the marine boundary layer are strongly impacted by reactions occurring at aqueous interfaces. Despite the potential importance of the air-sea interface in serving as a reactive surface, few direct field observations are available to assess its impact on reactive nitrogen deposition and halogen activation. Here, we present direct measurements of the vertical fluxes of the reactant-product pair N2O5 and ClNO2 to assess the role of the ocean surface in the exchange of reactive nitrogen and halogens. We measure nocturnal N2O5 exchange velocities (Vex = -1.66 ± 0.60 cm s(-1)) that are limited by atmospheric transport of N2O5 to the air-sea interface. Surprisingly, vertical fluxes of ClNO2, the product of N2O5 reactive uptake to concentrated chloride containing surfaces, display net deposition, suggesting that elevated ClNO2 mixing ratios found in the marine boundary layer are sustained primarily by N2O5 reactions with aerosol particles. Comparison of measured deposition rates and in situ observations of N2O5 reactive uptake to aerosol particles indicates that N2O5 deposition to the ocean surface accounts for between 26% and 42% of the total loss rate. The combination of large Vex, N2O5 and net deposition of ClNO2 acts to limit NOx recycling rates and the production of Cl atoms by shortening the nocturnal lifetime of N2O5. These results indicate that air-sea exchange processes account for as much as 15% of nocturnal NOx removal in polluted coastal regions and can serve to reduce ClNO2 concentrations at sunrise by over 20%.