Nitrogen speciation in various types of aerosols in spring over the northwestern Pacific Ocean

Abstract. The cumulative atmospheric nitrogen deposition has been found to profoundly impact the nutrient stoichiometry of the eastern China seas (ECSs: the Yellow Sea and East China Sea) and the northwestern Pacific Ocean (NWPO). In spite of the potential significance of dry deposition in those regions, shipboard observations of atmospheric aerosols remain insufficient, particularly regarding the compositions of water-soluble nitrogen species (nitrate, ammonium and water-soluble organic nitrogen – WSON). We conducted a cruise covering the ECSs and the NWPO during the spring of 2014 and observed three types of atmospheric aerosols. Aluminum content, air mass backward trajectories, weather conditions, and ion stoichiometry allowed us to discern dust aerosol patches and sea-fog-modified aerosols (widespread over the ECSs) from background aerosols (open ocean). Among the three types, sea-fog-modified aerosols contained the highest concentrations of nitrate (536 ± 300 nmol N m⁻³), ammonium (442 ± 194 nmol N m⁻³) and WSON (147 ± 171 nmol N m⁻³); furthermore, ammonium and nitrate together occupied  ∼  65 % of the molar fraction of total ions. The dust aerosols also contained significant amounts of nitrate (100 ± 23 nmol N m⁻³) and ammonium (138 ± 24 nmol N m⁻³) which were obviously larger than those in the background aerosols (26 ± 32 for nitrate and 54 ± 45 nmol N m⁻³ for ammonium), yet this was not the case for WSON. It appeared that dust aerosols had less of a chance to come in contact with WSON during their transport. In the open ocean, we found that sea salt (e.g., Na⁺, Cl⁻, Mg²⁺), as well as WSON, correlated positively with wind speed. Apparently, marine dissolved organic nitrogen (DON) was emitted from breaking waves. Regardless of the variable wind speeds from 0.8 to as high as 18 m s⁻¹, nitrate and ammonium, by contrast, remained in narrow ranges, implying that some supply and consumption processes of nitrate and ammonium were required to maintain such a quasi-static condition. Mean dry deposition of total dissolved nitrogen (TDN) for sea-fog-modified aerosols (1090 ± 671 µmol N m⁻² d⁻¹) was 5 times higher than that for dust aerosols (190 ± 41.6 µmol N m⁻² d⁻¹) and around 20 times higher than that for background aerosols (56.8 ± 59.1 µmol N m⁻² d⁻¹). Apparently, spring sea fog on the ECSs played an important role in removing atmospheric reactive nitrogen from the Chinese mainland and depositing it into the ECSs, thus effectively preventing its seaward export to the NWPO.