Abstract: The daily and seasonal atmospheric concentrations, deposition fluxes and emission sources of a few C3C9 gaseous alkyl nitrates (ANs) at the Belgian coast (De Haan) on the Southern North Sea were determined. An adapted sampler design for low- and high-volume air-sampling, optimized sample extraction and clean-up, as well as identification and quantification of ANs in air samples by means of gas chromatography mass spectrometry, are reported. The total concentrations of ANs ranged from 0.03 to 85 pptv and consisted primarily of the nitro-butane and nitro-pentane isomers. Air mass backward trajectories were calculated by the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to determine the influence of main air masses on AN levels in the air. The shorter chain ANs have been the most abundant in the Atlantic/Channel/UK air masses, while longer chain ANs prevailed in continental air. The overall mean N fluxes of the ANs were slightly higher for summer than those for winter-spring, although their contributions to the total nitrogen flux were low. High correlations between AN and HNO2 levels were observed during winter/spring. During summer, the shorter chain ANs correlated well with precipitation. Source apportionment by means of principal component analysis indicated that most of the gas phase ANs could be attributed to traffic/combustion, secondary photochemical formation and biomass burning, although marine sources may also have been present and a contributing factor.

Abstract: Daily and seasonal variations in dry and wet atmospheric nitrogen fluxes have been studied during four campaigns between 2004 and 2006 at a coastal site of the Southern North Sea at De Haan (Belgium) located at coordinates of 51.1723° N and 3.0369° E. Concentrations of inorganic N-compounds were determined in the gaseous phase, size-segregated aerosol (coarse, medium, and fine), and rainwater samples. Dissolved organic nitrogen (DON) was quantified in rainwater. The daily variations in N-fluxes of compounds were evaluated with air-mass backward trajectories, classified into the main air-masses arriving at the sampling site (i.e., continental, North Sea, and Atlantic/UK/Channel). The three, non-episodic campaigns showed broadly consistent fluxes, but during the late summer campaign exceptionally high episodic N-deposition was observed. The average dry and wet fluxes for non-episodic campaigns amounted to 2.6 and 4.0 mg N m−2 d−1, respectively, whereas during the episodic late summer period these fluxes were as high as 5.2 and 6.2 mg N m−2 d−1, respectively. Non-episodic seasons/campaigns experienced average aerosol fluxes of 0.91.4 mg N m−2 d−1. Generally, the contribution of aerosol NH4+ was more significant in the medium and fine particulate fractions than that of aerosol NO3−, whereas the latter contributed more in the coarse fraction, especially in continental air-masses. During the dry mid-summer campaign, the DON contributed considerably (15%) to the total N-budget. Exceptionally high episodic aerosol-N inputs have been observed for the late summer campaign, with especially high deposition rates of 3.6 and 2.9 mg N m−2 d−1 for Atlantic/UK/Channel and North Sea-continental (mixed) air-masses, respectively. During this pollution episode, the flux of NH4+ was dominating in each aerosol fraction/air-mass, except for coarse continental aerosols. High deposition of gaseous-N was also observed in this campaign with an average total N-flux of 22.5-times higher than in other campaigns.